Curable silicone composition and application and use thereof

Abstract

A curable composition comprising (A) an organopolysiloxane comprising a curable functional group; and (B) a silicone-free organic material containing a reactive functional group. The curable composition exhibits a high refractive index and optical transparency. The curable composition can be used to prepare cured materials exhibiting high refractive index, optical transparency, crack resistance, and low water vapor permeability.

Description

[0001] This application is a divisional of the application for Invention Patent Application with International Application Date of June 15, 2018, Chinese National Application No. 201880041812.7, and Invention Name of "Curable Silicone Compositions and Applications and Uses Thereof."

[0002] Cross Reference to Related Applications

[0003] 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. TECHNICAL FIELD

[0004] 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 non-silicone 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 transparency. The curable composition can be used in a variety of applications, including as a sealant, encapsulant, barrier coating, and the like, and can be applied in a variety of environments, including in electronic devices. BACKGROUND

[0005] Many new generation flexible printed electronic displays, such as organic light emitting diodes (OLEDs), organic photovoltaic displays (OPVs), organic thin film transistors (OTFTs), and the like, are extremely sensitive to water vapor and oxygen in the atmosphere, which limits the lifetime of the display device and its wide commercialization.

[0006] A current encapsulation technology commonly available in the field of moisture-sensitive organic electronic devices is the fixation of a glass lid with a getter material to the substrate by epoxy glue. The getter material, such as calcium oxide or barium oxide, is incorporated into the package to react with any by-products of the resin curing process or any residual water that is incorporated into the package or diffuses through the epoxy seal over time. Although glass has been commonly used as an encapsulant or barrier layer due to its low permeability to water vapor and oxygen, a major drawback of the glass encapsulation technology is that the resulting device becomes non-flexible and rigid, which does not meet the applications that require flexible devices.

[0007] Several attempts have been made to develop flexible barrier films. These include multilayer systems of alternating inorganic and organic layers (often more than 10 layers). Such systems are described, for example, in WO 00 / 36665 Al, WO 01 / 81649 Al, WO 2004 / 089620 A2, WO 03 / 094256 A2, and WO 2008 / 057045 Al. Although multilayer thin film technology provides good barrier properties and is useful for encapsulation purposes for electronic devices, the complex nature of thin film fabrication and high cost do not make them feasible in large area and mass manufacturing processes. Thus, it is desirable to provide substrates with improved barrier properties that can protect display devices from premature degradation and extend their lifetime. SUMMARY

[0008] The following presents a summary of the disclosure in order to provide a basic understanding of some aspects. This summary is not intended to identify key or important elements, nor is it intended to define any limitations of the various embodiments or claims. In addition, this summary can be

[0009] According to various aspects and embodiments, the present technology provides a curable silicone composition comprising an organopolysiloxane and an organic material free of silicone. The organopolysiloxane comprises an organic functional group in the backbone of the polysiloxane. It has been found that cured materials formed from compositions comprising such organopolysiloxanes exhibit relatively high refractive index, good optical transparency (e.g., low yellowing), flexibility, heat resistance, crack resistance, and / or moisture permeability.

[0010] In various aspects, the present invention provides a curable composition suitable for thin film flexible encapsulation technology that not only reduces the overall complexity but also provides a high quality barrier film that is scalable and easy to process for manufacturing large area display devices.

[0011] The present invention provides, in its aspects and embodiments, low moisture permeable silicone compositions that can provide cured materials with high refractive index and / or improved barrier properties suitable for organic electroluminescent display devices and extend their lifetime. In one aspect, the present invention provides a curable composition of a bicyclic modified organosilicon compound, wherein the bicyclic compound can be present in the terminal position of the silicone polymer, as a pendant group and / or in the backbone. Methods of making the bicyclic modified organosilicon compound and methods of making cured materials from the composition are disclosed.

[0012] In one aspect, the present invention provides a curable silicone composition comprising:

[0013] (A) an organopolysiloxane having the following formula:

[0014]

[0015] wherein 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 hydrocarbon-containing divalent organic group;

[0016] R 2 is a curable functional group independently selected from a vinyl group, a vinyl-containing group, an unsaturated hydrocarbon, an unsaturated cyclic hydrocarbon, an acrylate, a methacrylate, a hydroxyl group, an alkoxy group, and an epoxy group;

[0017] R 3 -R 14 is independently selected from hydrogen, a C1-C10 monovalent hydrocarbon group, a C6-C20 monovalent aromatic group, and a C4-C30 monovalent saturated or unsaturated cyclic alkyl group, a silicon-oxygen group containing 1-20 silicon atoms;

[0018] x and z are independently 1-30;

[0019] y and w are independently 0-30; and n is 1-30; and

[0020] (B) an organosilicon-free organic material comprising a reactive functional group.

[0021] In one embodiment of the curable organosilicon composition, R 1selected from the group consisting of C4-C30 ring-containing hydrocarbon groups selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1,1-divinylcyclohexane, 1,3-divinylcyclohexane, bicyclo[2.2.1]-2,5-divinylheptane, 1,4-di-2-prop-1-enylcyclohexane, 1,3-diisopropenylbenzene, spiro[5.5]-3,8-divinylundecane, 1,3-divinyladamantane, vinyl norbornene, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, pinane, bornane, 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.

[0022] In one embodiment of the curable silicone composition of any of the preceding embodiments, R 2 is selected from the group consisting of C1-C20 hydrocarbon groups comprising a vinyl functionality, monovalent C4-C20 branched hydrocarbon groups comprising a vinyl functionality, or monovalent C4 to C30 cyclic hydrocarbon groups comprising a vinyl functionality.

[0023] In one embodiment of the curable silicone composition of any of the preceding embodiments, R 2 is of the formula X-R 16 wherein X is a curable functionality selected from the group consisting of a vinyl group (CH2=CH2-), an unsaturated cyclic group, an unsaturated polycyclic group, and R 16is selected from the group consisting of cyclopentene, cyclohexene, cyclooctene, pinene, bornylene, 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[l. l.0]butene, bicyclo[2. l.0]pentene, bicyclo[2.2.0]hexene, bicyclo[3. l.0]hexene, bicyclo[3.2.0]heptene, bicyclo[3.3.0]octene, bicyclo[4. l.0]heptene, bicyclo[4.2.0]octene, bicyclo[4.3.0]nonene, bicyclo[4.4.0]decene, bicyclo[l. l. l ]pentene, bicyclo[2. l. l ]hexene, bicyclo[2.2. l ]heptene, bicyclo[2.2.2]octene, bicyclo[3. l. l ]heptene, bicyclo[3.2. l ]octene, bicyclo[3.2.2]nonene, bicyclo[3.3. l ]nonene, bicyclo[3.3.2]decene, bicyclo[3.3.3]undecene, adamantene, tricyclo[5.2. l.0 2,6 ]decene, tricyclo[4.3. l. l 2,5 ]undecene ring, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methylenadamantane, dicyclopentadiene, or (-)-β-cuparene, 4-vinylcyclohexyl.

[0024] In one embodiment of the curable silicone composition of any of the preceding embodiments, the organic material (B) is selected from a vinyl-terminated polyisobutylene. In one embodiment of the curable silicone composition of any of the preceding embodiments, the polyisobutylene has a number average molecular weight of from 200 to about 40,000. In one embodiment of the curable silicone composition of any of the preceding embodiments, the polyisobutylene has a number average molecular weight of from 900 to about 3,000.

[0025] In one embodiment of the curable silicone composition of any of the preceding embodiments, the curable composition comprises (C) a crosslinker selected from a compound comprising at least one -SiH group, at least one -SH group, or a combination of two or more thereof; (D) a reaction promoter 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.

[0026] In one embodiment of the curable silicone composition of any of the preceding embodiments, the crosslinker (C) is selected from a silicone-containing compound comprising 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.

[0027] In one embodiment of the curable silicone composition of any of the preceding embodiments, the reaction promoter is selected from a metal-containing catalyst.

[0028] In one embodiment of the curable silicone composition of any of the preceding embodiments, the inhibitor is selected from an olefinic compound, an acetylenic compound, or a combination thereof.

[0029] In one embodiment of the curable silicone composition of any of the preceding embodiments, the additive is selected from an antioxidant, a thermal stabilizer, an adhesion promoter, a filler, or a combination of two or more thereof.

[0030] In one embodiment of the curable silicone composition of any of the preceding embodiments, the composition has a refractive index of 1.45 to 1.51.

[0031] In one embodiment of the curable silicone composition of any of the preceding embodiments, the composition has a transparency of > 95%, even greater than 98%.

[0032] In one embodiment of the curable silicone composition of any of the preceding embodiments, the composition has a 10 -1 to 10 g / m 2 of MVTR, WVTR, O permeability per day.

[0033] In one aspect, the present application provides a cured article formed from the curable composition of any of the preceding embodiments.

[0034] In one aspect, the present application provides a cured article formed from the curable silicone composition comprising:

[0035] (A) an organopolysiloxane having the formula:

[0036]

[0037] wherein R 1 is a divalent hydrocarbon selected from C1-C20, C4-C20 branched divalent hydrocarbon, or C4-C30 divalent organic group containing cyclic hydrocarbon;

[0038] R 2curable functional groups independently selected from the group consisting of vinyl, vinyl-containing groups, unsaturated hydrocarbons, unsaturated cyclic hydrocarbons, acrylates, methacrylates, hydroxyl, alkoxy, and epoxy groups;

[0039] R 3 -R 14 independently selected from the group consisting of hydrogen, Ci-Cio monovalent hydrocarbon radicals, C6-C20 monovalent aromatic radicals, and C4-C30 monovalent saturated or unsaturated cyclic alkyl radicals;

[0040] x and z are independently 1-30;

[0041] y and w are independently 0-30; and

[0042] n is 1-30;

[0043] (B) an organosilicon-free organic material comprising a reactive functional group.

[0044] Optionally, the composition can comprise other components, such as (C) a crosslinker selected from the group consisting of a compound comprising at least one -SiH group, at least one -SH group, or a combination of two or more thereof; (D) a reaction promoter selected from the group consisting of 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.

[0045] In one embodiment, R 1selected from the group consisting of C4-C30 ring-containing hydrocarbon groups selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1,1-divinylcyclohexane, 1,3-divinylcyclohexane, bicyclo[2.2.1]-2,5-divinylheptane, 1,4-di-2-prop-1-enylcyclohexane, 1,3-diisopropenylbenzene, spiro[5.5]-3,8-divinylundecane, 1,3-divinyladamantane, vinyl norbornene, 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, 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.

[0046] In one embodiment of the cured article of any of the preceding embodiments, R 2 is a C1-C20 hydrocarbon group comprising a vinyl functionality, a monovalent C4-C20 branched hydrocarbon group comprising a vinyl functionality, or a monovalent C4 to C30 cyclic hydrocarbon group comprising a vinyl functionality.

[0047] In one embodiment of the cured article of any of the preceding embodiments, R 2 is of the formula X-R 16 , wherein X is a curable functionality and R 16 is a bond or a monovalent hydrocarbon group. In embodiments, R 16 may be a C1-C20 alkylene group, a C1-C10 alkylene group, or even a C1-C6 alkylene group, and X can be selected from the group consisting of a vinyl group (CH2=CH2-), an unsaturated cyclic group, an unsaturated polycyclic group.

[0048] In an embodiment, X is selected from the group consisting of cyclopentene, cyclohexene, cyclooctene, pinene, bornylene, 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[l.l.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[l.l.l]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 ]undecene ring, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methyleneadamantane, dicyclopentadiene, (-)-β-copaene, 4-vinylcyclohexyl.

[0049] In an embodiment of the cured article of any preceding embodiment, the crosslinking agent (B) is selected from the group consisting of a silicone-containing compound comprising at least one -SiH group, at least one -SH group, or a combination of two or more thereof.

[0050] In an embodiment, the silicone-containing compound is selected from the group consisting of a cyclic silicone, a linear silicone, a branched silicone, or a combination of two or more thereof.

[0051] In an embodiment of the cured article of any preceding embodiment, the reaction promoter is selected from a metal-containing catalyst.

[0052] In an embodiment of the cured article of any preceding embodiment, the inhibitor is selected from an olefinic compound or an acetylenic compound or a combination thereof.

[0053] In an embodiment of the cured article of any preceding embodiment, the additive is selected from an antioxidant, a heat stabilizer, an adhesion promoter, a filler, or a combination thereof.

[0054] In an embodiment of the cured article of any preceding embodiment, the article has a refractive index of 1.45 to 1.51.

[0055] In one embodiment of the cured article of any of the foregoing embodiments, the article has a transparency of > 95%, even greater than 98%.

[0056] In one embodiment of the cured article of any of the foregoing embodiments, the article has a transparency of 10 -1 to 10 g / m 2 • MVTR, WVTR, O permeability. In one embodiment, the cured article formed from the composition has a water vapor permeability of less than 3 g / m 2 • per day.

[0057] In one embodiment of the cured article of any of the foregoing embodiments, the article is selected from an LED encapsulant in electronic components or in combination with semiconductor devices, an optical waveguide, an optical lens, an optical bonding material, an optical adhesive, an optical film or sheet, a laminated film of sheets.

[0058] In another aspect, the present disclosure provides a personal care composition comprising the curable silicone composition of any of the foregoing embodiments. In one embodiment, the personal care composition is selected from a cosmetic preparation, a sunscreen, a shampoo, a hair conditioner, a skin lotion or cream. DETAILED DESCRIPTION

[0059] Reference will now be made to example embodiments. It should be understood that other embodiments can be used and structural and functional changes can be made. In addition, features of the various embodiments can be combined or altered. As such, the following description is presented in the context of illustrative embodiments only, and is not intended to limit the various alternatives and modifications that can be made to the illustrative embodiments described. In the disclosure, numerous specific details are provided to provide a thorough understanding of the disclosure. It should be understood that aspects of the disclosure can be practiced without all aspects necessary for inclusion in the disclosure.

[0060] As used herein, the words “instance” and “exemplary” mean an example or illustrative instance. The words “instance” or “exemplary” do not indicate a key or preferred aspect or embodiment. The word “or” is intended to be inclusive, not exclusive, unless the context clearly indicates otherwise. As an example, the phrase “A employs B or C,” includes any inclusive permutation of A employing a B or a C. As another example, the phrase “A employs B and C” includes any inclusive permutation of A employing B, C or both. As a further example, the phrase “A employs B, but not C” includes any non-exclusive permutation of A employing B, not C.

[0061] The present technology provides a curable composition comprising: (A) an organopolysiloxane comprising a curable functional group; and (B) an organic material free of silicone. The composition can also include other components such as, for example, (C) a crosslinker comprising a silyl hydride group or a thiol group; (D) a reaction promoter; (E) an inhibitor; and / or (F) other additives.

[0062] The organopolysiloxane (A) comprises a siloxane polymer having an organic functional group between silicon atoms in a portion of the main chain. The organopolysiloxane (A) comprises a compound of Formula (I):

[0063]

[0064] wherein R 1 is a divalent organic group selected from a C1-C20 hydrocarbon, a C4-C20 branched hydrocarbon, or a C4-C30 cyclic hydrocarbon-containing divalent hydrocarbon group;

[0065] R 2 is a curable functional group independently selected from a vinyl group, a vinyl-containing group, an unsaturated hydrocarbon, an unsaturated cyclic hydrocarbon, an acrylate, a methacrylate, a hydroxyl group, an alkoxy group, and an epoxy group;

[0066] R 3 -R 14 is independently selected from hydrogen, a C1-C10 monovalent hydrocarbon group, a C6-C20 monovalent aromatic group, and a C4-C30 monovalent saturated or unsaturated cyclic alkyl group, a siloxy group containing 1-20 silicon atoms; x and z are independently 1-30;

[0067] y and w are independently 0-30; and n is 1-30.

[0068] 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 (either removing two hydrogen atoms from the same carbon atom, or removing 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 embodiments, R 1 is selected from a C1-C6 linear or branched alkylene group.

[0069] R 1may be selected from divalent cyclic hydrocarbyl groups. As used herein, "cyclic" or "ring-containing" hydrocarbyl refers to a group derived by removing two hydrogen atoms from a ring-containing alkane, wherein (i) the two hydrogen atoms can be removed from the same ring carbon atom, (ii) one hydrogen atom is removed from one ring carbon and the other hydrogen atom is removed from another ring carbon, (iii) one hydrogen is removed from a ring carbon and one hydrogen is removed from a hydrocarbyl group attached to the chain, (iv) the two hydrogen atoms are removed from the same carbon atom of a hydrocarbyl group attached to the cyclic group, or (v) one hydrogen is removed from a first hydrocarbyl group attached to the cyclic group and one hydrogen is removed from a second hydrocarbyl group attached to the cyclic group.

[0070] The cyclic group in a ring-containing hydrocarbon can be a monocyclic hydrocarbyl group or a polycyclic hydrocarbyl group. Examples of suitable monocyclic hydrocarbyl groups include cycloalkyl groups having 3 to 12 carbon atoms, such as, but not limited to, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, or cycloalkenyl groups having 3 to 12 carbon atoms, such as cyclohexenyl. In embodiments, the monocyclic hydrocarbyl group is a monocyclic hydrocarbyl group having 3 to 7 carbon atoms. Cyclopentyl and cyclohexyl groups are particularly suitable.

[0071] Polycyclic hydrocarbyl groups include fused ring hydrocarbyl groups and crosslinked ring hydrocarbyl groups. Examples of fused ring hydrocarbyl groups include dicyclohexyl, perhydronaphthyl, and the like. Examples of crosslinked ring hydrocarbyl rings include, but are not limited to, for example, bicycloalkane rings, tricycloalkane rings, and tetracycloalkane rings, such as tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane and perhydro-1,4-methano-5,8-methanonaphthalene rings. Additionally, crosslinked ring hydrocarbyl rings include fused ring hydrocarbyl rings, for example, fused rings formed by the fusion of multiple 5- to 8-membered cycloalkane rings, such as perhydro naphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindenyl, perhydrophenarene rings.

[0072] may be part of an R 1 group or provides an R 1Examples of suitable 4-30 polycyclic hydrocarbyl groups for the R 2,6 ]decane tricyclo[4.3.1.1 2,5 ]undecane ring.

[0073] In embodiments, the ring-containing R 1 group can be represented by the formula: R 15 -A-R 15 where R 15 is a bond or a C1-C10 monovalent hydrocarbyl group, and A is a cyclic or polycyclic hydrocarbyl group. The cyclic or polycyclic group A can be a cyclic or polycyclic group as described above. It is understood that the R 15 group can be attached to the same ring carbon atom or different carbon atoms on the ring.

[0074] Examples of suitable groups for R 1 include, but are not limited to:

[0075]

[0076]

[0077] While the divalent organic group or “alkylene” type group of R 1 is described in terms of removal of hydrogen, it is understood by those skilled in the art of forming organosilicon-containing materials that the alkylene type group of R 1 can be derived and incorporated into the siloxane backbone by reacting a diene (conjugated or non-conjugated) compound containing the desired R 1 group with a suitable siloxane in the presence of a catalyst (e.g., Karstedt’s Catalyst).

[0078] R 2is a group comprising a curable functional group selected from a vinyl group, an acrylate group, a methacrylate group, a hydroxyl group, an alkoxy group, an alkenyloxy group, or an epoxy group. R 2 may be selected from a monovalent C1-C20 hydrocarbon group comprising a curable functional group, a monovalent C4-C20 branched hydrocarbon group comprising a curable functional group, or a monovalent C4 to C30 cyclic hydrocarbon group comprising a curable functional group. In embodiments, R 2 may be represented by the formula: X-R 16 wherein X is a curable functional group, and R 16 is a bond or a monovalent hydrocarbon group. In embodiments, R 16 may be a C1-C20 alkylene group; a C1-C10 alkylene group; or even a C1-C6 alkylene group. X can be selected from a vinyl group (CH2=CH2-), an unsaturated cyclic group, an unsaturated polycyclic group, and the like. In embodiments, X is selected from cyclopenetene, cyclohexene, cyclooctene, pinene, limanene, 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[l.l.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[l.l.l]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 ]undecene ring, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methylenadamantane, dicyclopentadiene, (-)-β- carene, 4-vinylcyclohexyl, and the like.

[0079] Examples of suitable R 2 or X groups include, but are not limited to:

[0080]

[0081] In embodiments, the polymer comprises an aromatic group attached to one of the silicon atoms, for example R 3-R 14 In embodiments, the R 5 and R 11 groups in the polymer comprise aromatic groups. In embodiments, the aromatic groups are phenyl groups. While not wishing to be bound by any particular theory, the presence of aromatic groups can be desirable to limit migration of silicon atoms.

[0082] In embodiments, the organopolysiloxane (A) comprises a polycyclic group and an aromatic group. The polycyclic group can be in the siloxane chain (e.g., R 1 ) and at the terminal end (i.e., R 2 ). In embodiments, the R 5 and R 11 groups in the polymer comprise aromatic groups. In one embodiment, the organopolysiloxane (A) is a compound of the following formula:

[0083]

[0084] In another embodiment, the organopolysiloxane (A) is a compound of the following formula:

[0085]

[0086] The non-silicone containing organic material (B) is selected from an organic monomer or oligomer having a reactive functional group. As used herein, the reactive functional group can also be referred to as a curable functional group. The reactive functional group can be selected from, but is not limited to, an ethylenically unsaturated monomer (e.g., allyl, vinyl, etc.), an ethylenically unsaturated aromatic compound, an ethylenically unsaturated acid, an ethylenically unsaturated anhydride, an acrylate, a methacrylate, an acrylamide, or a combination 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 methyldiglycol vinyl ether, corresponding allyl alkyl ethers, and combinations thereof. Non-limiting examples of ethylenically unsaturated acid and ethylenically unsaturated anhydride monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid, and anhydrides thereof, mono-vinyl ester of adipic acid, and combinations thereof. Non-limiting examples of olefin monomers include, for example, ethylene, propylene, butylene, isobutylene, pentene, cyclopentene, hexane, cyclohexene, octane, 1,3- butadiene, chlorobutadiene, cyclobutadiene, isoprene, and combinations thereof. Non-limiting examples of ethylenically unsaturated aromatic compounds include, for example, styrene, alkyl styrenes, and chlorostyrene.

[0087] In one embodiment, the organic material (B) is selected from a functionalized isobutylene compound. The polyisobutylene can have a number average molecular weight Mn In embodiments, the polyisobutylene has a number average molecular weight M n As used herein, the term "polyisobutylene" also includes oligomeric isobutylenes, such as di-, tri-, tetra-, penta-, hexa-, and hepta-isobutylenes.

[0088] The reactivity of the polyisobutylene increases with increasing concentration of reactive functional groups. In embodiments, the polyisobutylene comprises at least 50 mol% of reactive functional groups; at least 60 mol% of reactive functional groups; even at least 80 mol% of reactive functional groups. In one embodiment, the polyisobutylene comprises at least 50 mol% of terminal double bonds based on the total number of polyisobutylene macromolecules; at least 60 mol% of terminal double bonds based on the total number of polyisobutylene macromolecules, even at least 80 mol% of terminal double bonds. The terminal double bonds can be vinyl double bonds [CH=C(CH3)2] (beta-olefins) or vinylidene double bonds [CH— C(=CH2)— CH3] (alpha-olefins). A substantially homopolymerized polyisobutylene base can have a uniform polymer backbone. In embodiments, the polyisobutylene system is formed to the extent of at least 85 wt% of isobutylene units of the repeating unit [CH2C(CH3)2-], at least 90 wt%, even at least 95 wt%.

[0089] In embodiments, the polyisobutylene can have a polydispersity index (PDI) of 1.05 to 10, 1.05 to 3.0, even 1.05 to 2.0. Polydispersity refers to the ratio of the weight average molecular weight M w to the number average molecular weight M n (PDI = M w / M n ).

[0090] Polyisobutylenes suitable for use in the composition include all polymers obtainable by cationic polymerization and comprise at least 60 wt% of isobutylene, at least 80 wt%, at least 90 wt%, even at least 95 wt% in copolymerized form. Furthermore, the polyisobutylene can comprise other butene isomers such as 1-butene or 2-butene, and different olefinically unsaturated monomers copolymerizable with isobutylene under cationic polymerization conditions in copolymerized form.

[0091] Suitable isobutylene feedstocks for making polyisobutylenes include isobutylene itself and isobutylene C4 hydrocarbon streams, such as C4 raffinate, C4 fractions from isobutylene dehydrogenation, C4 fractions from steam crackers, FCC crackers (FCC: fluidized bed catalytic cracking), provided that they have been substantially freed of 1,3-butadiene present therein. Particularly suitable C4 hydrocarbon streams contain generally less than 500 ppm, preferably less than 200 ppm, of butadiene. When C4 fractions are used as starting materials, hydrocarbons other than isobutylene act as inert solvents.

[0092] Useful monomers that can be copolymerized with isobutylene include vinyl aromatic compounds such as styrene and a-methylstyrene, Ci-C4-alkylstyrenes such as 2-, 3- and 4-methylstyrene, and 4-tert-butylstyrene, isoolefins having 5 to 10 carbon atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1.

[0093] Examples of polyisobutylenes suitable for use in the composition include, but are not limited to: Glissopal® brand, such as Glissopal 550, Glissopal 1000 and Glissopal 2300, from BASF Aktiengesellschaft, Ludwigshafen, Germany, and Oppanol® brand, such as Oppanol B10, B12 and B15, from BASF Aktiengesellschaft, Ludwigshafen, Germany. Glissopal 550, Glissopal 1000 and Glissopal 2300, and Oppanol® brand, such as Oppanol B10, B12 and B15, from BASF Aktiengesellschaft, Ludwigshafen, Germany. Glissopal 550, Glissopal 1000 and Glissopal 2300, and Oppanol® brand, such as Oppanol B10, B12 and B15, from BASF Aktiengesellschaft, Ludwigshafen, Germany.

[0094] In another embodiment, the organic material (B) can be selected from an acrylate monomer, an acrylate oligomer, or a combination thereof. As used herein, the acrylate monomer or acrylate oligomer refers to a monomer or oligomer containing one or more acryloyl groups, one or more methacryloyl groups, or one or more acryloyl groups and one or more methacryloyl groups, respectively. In one embodiment, the acrylate monomer or oligomer can be an epoxy acrylate, a urethane acrylate, an aminated acrylate, or the like. It is understood that the monomer and / or oligomer can contain one or more acryloyl or methacryloyl groups, such that they can be mono-, di-, tri-, or the like acrylates.

[0095] In an embodiment, the organic material (B) can include an acrylate monomer. Examples of suitable acrylate monomers include, but are not limited to, 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, alkyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, epoxy cyclohexylmethyl methacrylate, ethylene glycol phenyl ether methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, methyl adamantyl methacrylate, methyl methacrylate, methyl glycidyl methacrylate, isobutyl acrylate, t-butyl acrylate, lauryl acrylate, alkyl acrylate, 2-hydroxy acrylate, trimethoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-fluoroethyl acrylate, 4-fluoropropyl acrylate, and triethylsiloxyethyl acrylate, or a combination of two or more thereof.

[0096] In an 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, alicyclic, aromatic, heterocyclic, and / or epoxy functionality. In some embodiments, a saturated long chain alkyl (meth)acrylate, alicyclic (meth)acrylate, (meth)acrylate / epoxy monomer, or a combination thereof can be used as a monomer. The multifunctional (meth)acrylate monomer can be unsubstituted or substituted with various groups such as hydroxyl or alkoxy groups.

[0097] 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 resin. Exemplary alicyclic (meth)acrylates include, but are not limited to, isobornyl (meth)acrylate, tetramethylpiperidinyl methacrylate, pentamethylpiperidinyl methacrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanediol di(meth)acrylate, tricyclodecanediethanol (di(meth)acrylate), and methacrylated epoxides.

[0098] Examples of commercially available acrylate monomers include, but are not limited to, acrylate monomers with trade names such as those produced by Enteral. or

[0099] In another embodiment, the organic material (B) may include acrylate oligomers. Examples of suitable acrylate oligomers include, but are not limited to, those with a molecular weight of about 1,000 to 100,000. In embodiments, the acrylate oligomer may be selected from polyester (meth)acrylates, urethane (meth)acrylates, alkoxylated (meth)acrylate oligomers, epoxy (meth)acrylates, amination (meth)acrylates, (meth)acrylated (meth)acrylic acids, or combinations of two or more thereof.

[0100] 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 diacrylates or phenolic epoxy acrylates, or mixtures of two or more thereof.

[0101] Suitable examples of commercially available acrylate oligomers include, but are not limited to, acrylate oligomers with trade names such as those produced by Sartomer. or Manufactured by Eternal or and manufactured by UCB or

[0102] Examples of suitable polyester (meth)acrylates include, but are not limited to, acrylated epoxidized soybean oil compounds such as (Cytec), fatty acid containing polyester (meth)acrylates such as 870, 657, 450 (Cytec), and polyester (meth)acrylates such as 800, 884, 810 and 830 (Cytec).

[0103] Examples of suitable epoxy (meth)acrylates include, but are not limited to, di(meth)acrylates of the diglycidyl ether of bisphenol A (BADGED(M)A), and modifications thereof (see, for example, EPOXY EPOXAMINE® from Cytec 3700 or 600, 3701, 3703, 3708 and 3639). Examples of suitable urethane (meth)acrylates include, but are not limited to: 284, 264, 210, 230, 1290 (Cytec). Examples of suitable aminated (meth)acrylates include, but are not limited to: 80, 81, 83, 7100, P115, and others. Examples of suitable (meth)acrylic (co)polymers that can be used include, but are not limited to 745 and / or 1200. Examples of suitable inert polyesters include, but are not limited to 525 and its optional chlorinated variants (such as 436 and others).

[0104] The crosslinking agent (C) comprises a functional group that is reactive with the curable functional group of the organopolysiloxane (a). In embodiments, the crosslinking agent (b) comprises a Si-H group, a S-H group, a vinyl group, a vinyl-containing group, an unsaturated hydrocarbon, an unsaturated cyclic hydrocarbon, an acrylate, a methacrylate, a hydroxyl group, an alkoxy group, an epoxy group, or a combination of two or more thereof. In embodiments, the crosslinking agent is selected from a linear, branched, or cyclic organosilicon material comprising a Si-H or S-H group. It is understood that combinations of different crosslinking agent compounds can be used as desired.

[0105] In embodiments, the crosslinker (C) is selected from silyl hydrides. The silyl hydrides are not particularly limited. In embodiments, the silyl hydrides can be selected from the group consisting of compounds of 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 combinations of two or more thereof. R 17 is independently at each occurrence C1-C18 alkyl, C1-C18 substituted alkyl, wherein R 17 optionally contains at least one heteroatom, g has independently at each occurrence a value of 0 to 3, f has a value of 1 to 8, k has a value of 0 to 3000, each of p, u, v, r, and e independently has a value of 0 to 20, t and s are 0 to 3000, with the proviso that p + s + r equals 1 to 1000, and the valency of all elements in the silyl hydride is satisfied. As used herein, M represents a monofunctional group of the formula R 18 3SiO 1 / 2 , D represents a difunctional group of the formula R 18 2SiO 2 / 2 , T represents a trifunctional group of the formula R 18 SiO 3 / 2 , Q represents a tetrafunctional group of the formula SiO 4 / 2 , and MH represents HR 18 2SiO 1 / 2 , T H represents HSiO 3 / 2 , D H represents R 18 HSiO 2 / 2 ; R 18 each occurrence is independently C1-C18alkyl, C1-C18substituted alkyl, wherein R 18 optionally contains at least one heteroatom; h is 1-8, and j is 0-10.

[0106] Some non-limiting examples of silyl hydride include methylhydrogensiloxy dimethylsiloxane copolymers, including those from Gelest, such as HMS 501 HPM-502, HMS-992, HMS-064, polyhydrosilsesquioxane, and other hydride-containing copolymers or homopolymers of dimethylsiloxane or phenyl-containing siloxanes. Other suitable silyl hydrides include those present in SYLGARD 184, a two-part silicone available from Dow Corning, Midland, Mich, which is provided without the thermal hydrosilylation catalyst that is typically included in the commercial form.

[0107]

[0108] HMS-501 - Methylhydrogensiloxy dimethylsiloxane copolymer

[0109] The following structure shows one example of an organohydrogenpolysiloxane having phenyl functionality (HDP-111 - hydride-terminated polyphenyl(dimethylhydrogensiloxy)siloxane, available from Gelest Inc., Tullytown, Pa.).

[0110]

[0111] HDP-111 - hydride-terminated polyphenyl(dimethylhydrogensiloxy)siloxane

[0112] Examples of other silyl hydride reagents include Q resins, which can 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 TM (Clariant LSM Corporation), 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 TM(Gelest), 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 TM (Gelest), 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.

[0113] Examples of suitable mercapto-functional siloxanes include, but are not limited to, products such as Shin-Etsu Chemical Co., Ltd.'s KF-2001 and KF-2004; Gelest's SMS-022, SMS-042, and SMS-992; United Chemical's PS848, PS849, PS849.5, PS850, PS850.5, and PS927; and B 7610 available from Momentive Performance Materials Inc.

[0114] The crosslinking agent (C) can also be selected from a compound of the formula:

[0115]

[0116] where R 19 is a divalent organic radical selected from a C1-C20divalent hydrocarbon, a C4-C20branched divalent hydrocarbon, or a C4-C30divalent cyclic-containing hydrocarbon radical;

[0117] R 20 is a functional group selected from hydrogen, an acrylate, a methacrylate, a thiol, or R 2 ;

[0118] R 21 -R 32 is independently selected from hydrogen, a C1-C10monovalent hydrocarbon radical, a C6-C20monovalent aromatic radical, and a C4-C30monovalent cyclic alkyl radical;

[0119] a and d are independently 1-30;

[0120] b and c are independently 0-30; and m is 1-30.

[0121] R 19 may be selected from any radical suitable as the R 1 radical above, R 21 -R 32 may be selected from any radical suitable as the R 3 -R 14 radical above. However, the details of these radicals are not repeated for the sake of brevity.

[0122] The composition includes a reaction promoter (D) that acts to cure the organopolysiloxane (A), the organic material (B), and the crosslinking agent (C). The reaction promoter (D) can be, for example, a photoinitiator, a thermal initiator, a metal catalyst, or a combination of two or more thereof.

[0123] In embodiments, the reaction promoter comprises a catalyst, such as a hydrosilylation catalyst. Useful catalysts include those compounds or molecules that can catalyze the hydrosilylation reaction between a reactive SiH-containing moiety or substituent and a carbon-carbon bond, such as a carbon-carbon double bond. Further, in one or more embodiments, these catalysts can be soluble in the reaction medium. The types of catalysts include transition metal compounds, including those compounds comprising Group VIII metals. Exemplary Group VIII metals include palladium, rhodium, germanium, and platinum. Exemplary catalyst compounds include chloroplatinic acid, elemental platinum, chloroplatinic acid hexahydrate, a complex of chloroplatinic acid with sym-di-vinyltetramethyldisiloxane, dichloro-bis(triphenylphosphine)platinum(II), cis-dichloro-bis(acetonitrile)platinum(II), dicarbonyl dichloroplatinum(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 carrier such as alumina, silica or carbon black, platinum-vinylsiloxane complexes (e.g., Pt n (ViMe2SiOSiMe2Vi) n and Pt[(MeViSiO)4] m ), platinum-phosphine complexes (e.g., Pt(PPh3)4and Pt(PBu3)4) and platinum-phosphite complexes (e.g., Pt[P(Oph)3]4and Pt[P(Obu)3]4), where Me represents methyl, Bu represents butyl, "Vi" represents vinyl and 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, and the like.

[0124] In embodiments, a photoinitiator can be employed as the reaction promoter to promote the curing of the siloxane. The photoinitiator can be selected as desired for a particular purpose or intended application. Examples of suitable photoinitiators include, but are not limited to, benzophenone, phosphine oxide, nitroso compound, acryloyl halide, hydrazone, mercapto compound, pyrillium compound, triacryloyl imidazole, benzimidazole, chloroalkyl triazine, benzoin ether, benzil ketals, thioxanthone, camphorquinone, acyl phosphine, and phenylacetophenone derivatives.

[0125] In one embodiment, the photoinitiator is selected from acylphosphine. The acylphosphine may be mono- or bis-acylphosphine. Examples of suitable acylphosphine oxides include those described in U.S. Patent 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 (… TPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide ( TPO, from LAMBERTI Chemical Specialties in Galarat, Italy; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (available from Albemarle in Baton Rouge, Louisiana, USA). HMPP), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (available from BASF (Ludwigsafen, Germany)). TPO), diphenyl (2,4,6-trimethylbenzoyl)phosphonate ( TPO-L), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (available from CibaSpecialty Chemicals, Asphaltville, New York). 819), and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (e.g. from Ciba) Incorporation with α-hydroxy ketones 1700 1800 and 1850).

[0126] Examples of α-hydroxy ketone photoinitiators may include 1-hydroxy-cyclohexylphenyl ketone ( 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone ( 1173) and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone ( 2959), all of which are available from Ciba Specialty Chemicals (New York Asphalt Village).

[0127] Examples of α-aminoketone photoinitiators may include 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone ( 369) and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone ( Both (907) are available from Ciba Specialty Chemicals (Asphalt Village, New York).

[0128] The curable composition can optionally comprise a polymerization inhibitor (E). The polymerization inhibitor is not particularly limited and can be selected as needed depending on the particular purpose or intended use. Inhibitors of platinum group metal catalysts of component (E) are well known in the silicone art. Examples of suitable inhibitors include, but are not limited to: olefinically unsaturated amides, aromatic unsaturated amides, acetylenic compounds, olefinically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or isolated ene-yne, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphites, nitrites, diaziridines, and the like. Particularly suitable inhibitors for the composition are acetylenic alcohols and maleates. Examples of suitable polymerization inhibitors include, but are not limited to: diallyl maleate, hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine, and the like.

[0129] The amount of component (E) in the composition is not critical and can be any amount that retards the above platinum catalyzed hydrosilylation reaction at room temperature, while not preventing the reaction at moderately elevated temperatures, i.e., temperatures from 25 to 125 °C above room temperature. No particular amount of inhibitor is suggested to obtain a particular bath life at room temperature, since the required amount of any particular inhibitor used depends on the concentration and type of platinum metal containing catalyst, the nature and amount of components a and b. Component (E) can range from 0 to about 10 wt%, from about 0.001 wt to 2 wt%, even from about 0.12 to about 1 wt%. Here, as elsewhere in the specification and claims, numerical values can be combined to form new and alternative ranges. In one embodiment, the composition can be free of any inhibitor component (E).

[0130] The curable composition can further comprise an additive (F). Other additives can include, but are not limited to: adhesion promoters, antioxidants, fillers, pigments, dyes, filler treating agents, plasticizers, spacers, extenders, biocides, stabilizers, flame retardants, surface modifiers, anti-aging additives, rheological additives, corrosion inhibitors, surfactants, or combinations thereof.

[0131] Various organofunctional silane and siloxane adhesion promoters to inorganic substrates can be used in the composition. Suitable silanes include, but are not limited to: aminosilanes, epoxysilanes, isocyanate silanes, mercaptosilanes, iminosilanes, anhydride silanes, carboxylate functional siloxanes, and the like. Combinations of various types of adhesion promoters can also be used. Such components typically hinder cure via metal catalyzed hydrosilylation. Suitable adhesion promoters include, but are not limited to various aminosilane materials such as 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, available from Momentive Performance Materials.

[0132] The curable composition can also include an antioxidant compound. Examples of suitable classes of antioxidant compounds include, but are not limited to, hindered amines and / or hindered phenol compounds.

[0133] Examples of hindered amine antioxidant compounds include, but are not limited to: hindered amine light stabilizer (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, polycondensation product of dibutylamine-1,3,5-triazine-N,N'-bis-(2,2,6,6-tetramethyl-4- piperidyl)-1,6-hexamethylenediamine-N-(2,2,6,6-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}], polymer of dimethyl succinate with 4-hydroxy-2,2,6,6-tetramethyl-1 -piperidinethanol, [reaction product of decanedioic acid bis(2,2,6,6-tetramethyl-1 (octyloxy)-4-piperidyl) ester, 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-4-piperidyl) sebacate, 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, and the like.

[0134] In one embodiment, the antioxidant compound is a hindered phenolic compound. The hindered phenol can be selected as desired for a particular purpose or intended application. Examples of suitable hindered phenols include, but are not limited to, monophenols such as 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, and 2,6-tert-butyl-4-ethylphenol, bisphenols such as 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), and polymeric phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis(4'-hydroxy-3-tert-butylphenyl)butanoic acid diol ester, and tocopherols (vitamin E), pentaerythritol-tetrakis[3-(3,5-di-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 -methylpentadecyl)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)tris-p-cresol, calcium diethylbis[[[3,5-bis-(1,1 -dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate], 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)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-(1 H,3H,5H)-trione, reaction products of N-phenylalanine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, and the like.

[0135] IRGANOX 1330 is a sterically hindered phenolic antioxidant commercially available from BASF ("3,3',3',5,5',5'-Hexa-tert-butyl-a,a',a'-(mestilyl-2,4,6-triyl)tri-p-cresol"). Irganox 1010 is a sterically hindered phenolic antioxidant commercially available from BASF ("Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)") or as ETHANOX TM 330commercially available 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene (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 as Irganox 3114.

[0136] The curable composition can optionally include a light stabilizer. The light stabilizer is not particularly limited and can be selected as needed for a particular application or intended use. Examples of suitable materials for light stabilizers 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-amylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, reaction products of 3-(3-(21-1-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionic acid / polyethylene glycol 300, 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.

[0137] The curable composition can include the organopolysiloxane (A) in an amount of about 5 to about 98 mass %, about 10 to about 90 mass %, or about 20 to about 80 mass %. The curable composition can include the organic material (B) in an amount of about 2 to about 95 mass %, about 10 to about 90 mass %, or about 20 to about 80 mass %. The crosslinker (C) can be present in an amount of about 2 to about 25 mass %, about 6 to about 20 %, or about 6 to about 12 mass %. The reaction promoter (C) can be present in an amount of about 0.0001 to about 0.2 mass %, about 0.0002 to about 0.05 mass %, or about 0.0005 to about 0.02 mass %. The inhibitor (D) can be present in an amount of about 0.0001 to about 1 mass %, about 0.0002 to about 0.6 mass %, or about 0.0005 to about 0.3 mass %. The adhesion promoter can be present in an amount of about 0.1 to about 10 mass %, about 0.3 to about 5 mass %, or about 0.5 to about 3 mass %.

[0138] The curable composition has various properties that can make the composition and cured materials formed therefrom useful for 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.

[0139] The curable composition can also exhibit excellent optical clarity. In embodiments, the curable composition has a transparency of about 95% or greater, about 96% or greater, about 97% or greater, about 98% or greater, even about 99% or greater, at 400 nm to about 800 nm.

[0140] Additionally, the viscosity of the composition can be controlled or adjusted as desired within a wide range of viscosities to allow control of the processing of the composition as can be desired for the intended application. In embodiments, the viscosity of the curable composition can be about 0.2 to about 43 Pa.s, about 1 to about 35 Pa.s, about 5 to about 25 Pa.s, even about 10 to about 20 Pa.s.

[0141] Curing the curable silicone composition of the present application produces a cured product having high hardness and excellent transparency, crack resistance, and heat resistance. The curing conditions are not particularly limited and vary depending on the amount of the composition, but the curing temperature is preferably in the range of 60 to 180°C, and the curing time is typically in the range of 0.5 to 10 hours. In embodiments, the curing can be completed after 30 minutes at a temperature of about 100°C. Curing can also be accomplished by UV curing according to standard procedures for exposure to UV radiation.

[0142] The cured material formed from the curable composition can also exhibit desirable properties for a variety of applications. In embodiments, the curable composition can have a refractive index greater than about 1.40. In embodiments, the curable composition has a refractive index of about 1.40 to about 1.60, about 1.42 to about 1.58, even 1.45 to about 1.50.

[0143] The cured material can also exhibit excellent optical transparency. In embodiments, a 1 mm thick piece of the cured material has a transparency of about 95% or greater, about 96% or greater, about 97% or greater, about 98% or greater, even about 99% or greater, from 400 nm to about 800 nm.

[0144] The cured material can also exhibit high thermal stability and resistance to cracking, as evaluated and understood by various acceptable test methods, including but not limited to adhesion after water immersion, critical strain, abrasion, micro-indentation testing, and the like.

[0145] The cured material can also exhibit good water vapor permeability. In embodiments, a 1 mm thick piece of the cured material has a water vapor permeability of about 0.1 to about 15 g / m 2 • day under JIS Z0208 test method. This can also be referred to as moisture vapor transmission rate, water vapor transmission rate, oxygen permeability (MVTR, WVTR, O permeability). The moisture vapor transmission rate, water vapor transmission rate, oxygen permeability can be about 0.1 to about 15 g / m 2 • day, about 0.5 to about 10 g / m 2 • day, about 1 to about 7.5 g / m 2 • day, about 2 to about 5 g / m 2 • day. In one embodiment, the moisture vapor transmission rate, water vapor transmission rate, oxygen permeability is about 10 to about 15 g / m 2 • day. Here, as elsewhere in the specification and claims, numerical values can be combined to form new and unrecited ranges.

[0146] The curable silicone compositions of the present application can be used as curable silicone materials, encapsulation materials for optical devices such as optical elements, encapsulation materials for other electronic devices such as semiconductor elements, and electrically insulating coating materials. Examples of optical devices include optical elements such as LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, and CCDs; and optical elements such as lenses, bonding materials, adhesives, films, sheets, and the like. The cured material can 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.

[0147] The curable silicone composition can be included in a personal care composition, such as, but not limited to, a cosmetic, a sunscreen, a hair product such as a shampoo or a hair conditioner, a skin care lotion, a cream, and the like. The personal care composition can include various ingredients such as carriers, pigments, film formers, emulsifiers, vitamins, plasticizers, surfactants, antioxidants, waxes, oils, solvents, and the like.

[0148] In one embodiment, the personal care product can optionally contain 0-90 parts by weight of a 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 which are extended with solid diluents or are organic pigments prepared by precipitation of a water-soluble dye on an adsorptive surface, usually aluminum hydroxide. Lakes are also formed from the precipitation of insoluble salts of acid or basic dyes. Calcium lakes and barium lakes are also useful 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 can also be included in the composition, such as pearls, titanium oxide, Red 6, Red 21, Blue 1, Orange 5, and Green 5 dyes, chalk, talc, iron oxide, and titanated mica.

[0149] The personal care composition can optionally contain 0-99 parts by weight of an organic film former known in the art. The film former can be any film former which is cosmetically acceptable. Examples of useful film formers include natural waxes, polymers such as polyethylene polymers, and PVP, ethylene vinyl acetate, dimethicone gums and resins such as shellac, copolymers of polyterpenes.

[0150] The personal care composition can optionally include 0-50 parts by weight of 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 dioxides, zinc oxides and / or zirconium oxides, BaTiO3, CaTiO3, SrTiO3, and SiC. Absorbing sunscreens, which are generally organic, are particularly useful. Such absorbing sunscreens include, but are not limited to: UV-A absorbers that generally absorb radiation in the 320 to 400 nm region of the ultraviolet spectrum, such as anthranilates, benzophenones and dibenzoylmethanes; and UV-B absorbers that 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 octisalate, dioxybenzone, homosalate, menthyl anthranilate, octocrylene, octyl methoxycinnamate, octyl salicylate, oxybenzone, padimate, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, amino benzoic acid, amyl dimethyl p-aminobenzoic acid, diethanolamine p-methoxycinnamate, digalloyl trioleate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl salicylate, glyceryl aminobenzoate, homomenthyl salicylate, homosalate, 3-imidazol-4-yl acrylate and its ethyl ester, methyl anthranilate, octyl dimethyl PABA, 2-phenylbenzimidazole-5-sulfonic acid and salts, sulisobenzone, trolamine salicylate, N,N,N-trimethyl-4-(2-oxo-2-oxo-3-ylmethyl)aniline methyl sulfate, aminobenzoate, 4-isopropylbenzyl salicylate, 2-ethylhexyl 4-methoxycinnamate, methyl diisopropyl cinnamate, isoamyl 4-methoxycinnamate, diethanolamine 4-methoxycinnamate, 3-(4'-trimethylammonium)-benzylidene-boman-2-onemethylsulfate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy-4'-methoxybenzophenone, ca-(2-oxo-2-oxo-3-yl)-tolyl-4-sulfonic acid and its soluble salts, 3-(4'-sulfo)benzylidene-camphor and its soluble salts, 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, benzophenone 1,4-bis(3-methylene-10-camphorsulfonic) acid and its salts, urocanic acid, 2,4,6-tris-(2'-ethylhexyl-1 '-oxycarbonyl)aniline 1,3,5-triazine, 2-(p-tert-butylamido)aniline-4,6-bis-(p-(2'-ethylhexyl 1 '-oxycarbonyl)aniline-1,3,5-triazine, 2,4-bis{1,4-(2-ethylhexyloxy)-2-hydroxy-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, polymers of N-(2et 4)-(2-oxo-benzylidene) methyl benzyl acrylamide, 1,4-bisbenzimidazolyl- phenylene-3,3',5,5'-tetrasulfonic acid and its salts, benzal malonate substituted polyorganosiloxanes, benzotriazole substituted polyorganosiloxanes (Drometrizole Trisiloxane), solubilized 2,2'-methylene-bis-1,6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyl dibenzoylmethane, 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 foregoing sunscreen agents.

[0151] In particular, the personal care composition can be formulated for use as, but not limited to, a color cosmetic, a sunscreen, a hair conditioner, a moisturizer, and the like. Suitable forms and formulations for such applications are known to those of ordinary skill in the art. For example, when formulated for use as a sunscreen, the composition can be in the form of an emulsion, microemulsion, or nanoemulsion. Further, the emulsion can be a fluid simple emulsion, a fluid multiple emulsion, a rigid simple emulsion, or a rigid multiple emulsion. The simple or multiple emulsion can comprise a continuous aqueous phase containing dispersed lipid vesicles or oil droplets, or a continuous fatty phase dispersed lipid vesicles or water droplets. In one embodiment, the sunscreen application is an emulsion having a continuous aqueous phase, and can be in the form of a stick, a skin lotion, a gel, a spray, and the like. Suitable emulsifiers for forming the sunscreen emulsion include, for example, ethoxylated surfactants known in the art, such as polysorbate-20, laureth-7, laureth-4, Brij® 98, Brij® 58, and Brij® 35, which are available from SEPPIC, and the like. 305, oils such as vegetable and mineral oils; animal and / or synthetic waxes, such as beeswax, paraffin wax, rice wax, candelilla wax, carnauba wax, and derivatives thereof; and hydrocarbon gels or bentone-type gels, such as Gel SS71, Gel EA2786, Quaternium-18 bentone, 38CE, Gel ISD V, or Gel ISD; and silicone emulsifiers, such as Hexadecyl Polydimethylsiloxane Copolyol-Polyglyceryl 4-Isostearate-Hexyl Laurate (K-4) available from Goldschmidt Chemical Corporation. WE09), behenyl alcohol, EM 90), (EM 7), lauryl methicone copolyol (5200), cyclomethicone and dimethicone copolyol (DC5225C and DC3225C), cyclopentasiloxane and dimethicone copolyol (SF1528).

[0152] The personal care composition can optionally comprise a vitamin or skin nutrient agent. Some suitable agents are ceramides, hyaluronic acid, panthenol, peptides (copper hexapeptide-3), AHA's (lactic acid), retinol (retinyl palmitate) -Vit. One derivative, vitamin C (L-ascorbic acid), BHA's (salicylic acid), tea (green, white, black), soy and other plant derivatives, isoflavones (grape seed extract), hexapeptide-6, acai berry.

[0153] A plasticizer can also be added to the formulation to improve the flexibility and cosmetic properties of the resulting formulation. Plasticizers are often used to avoid the brittleness and cracking of film formers and include, for example, lecithin, polysorbate, dimethicone copolyol, glycol, citrate ester, glycerin, and dimethicone. The amount of plasticizer needed can be routinely varied by one skilled in the art based on the desired properties and contemplated application.

[0154] The compositions of the present application can be incorporated into a carrier, such as a volatile carrier that rapidly volatilizes upon application. The volatile carrier can be selected from volatile hydrocarbons, volatile silicones, and mixtures thereof.

[0155] Hydrocarbon oils useful in personal care products include those having a boiling point in the range of 60-260°C, including those having a boiling point in the range of about C8to about C 20 hydrocarbon oils having a chain length of even C8to C 20 isoparaffins. Examples include isododecane, isohexadecane, isoeocosane, 2,2,4-trimethylpentane, 2,3-dimethylhexane, and mixtures of two or more thereof.

[0156] ​Suitable volatile silicone fluids include cyclic polydimethylsiloxanes having 3, 4, and 5 membered ring structures corresponding to the formula (R2SiO)x x wherein x is about 3 to about 6.

[0157] The above description includes examples of the specification. Of course, it is not possible to describe every conceivable combination of components or methodologies for describing the specification, but one of ordinary skill in the art can recognize that many further combinations and permutations of the specification are possible. Accordingly, the specification is intended to embrace all such alterations, modifications, and variations which fall within the spirit and scope of the appended claims. Additionally, where the term "including" is used in the detailed description or claims, such term is intended to be inclusive in a manner similar to the term "comprising" as that term is interpreted when used as a transitional word in a claim.

[0158] EMBODIMENTS

[0159] Aspects of the disclosure will now be described and further understood with respect to the following embodiments. These embodiments are illustrative only and should not be construed as limiting the application disclosed herein to the materials or process parameters, equipment, or conditions described.

[0160] Example 1: Preparation of Component (A-1)

[0161] Component A-1 can be prepared according to the following procedure.

[0162] A norbornene-terminated phenylmethylsiloxane norbornene ethyl block copolymer (A-1) having a molecular weight of 3 kD was synthesized according to the following scheme:

[0163] Into a 500 mL three necked round bottom flask equipped with a reflux condenser, a dropping funnel and a mechanical stirrer, 100 mL of toluene and 5-vinylbicyclo[2.2.1]hept-2-ene (128.7 g, 1.07 mol) were added under nitrogen atmosphere. To this solution, 0.289 g of Karstedt catalyst (15 ppm of 2 wt% Pt) was added. The whole apparatus was kept in an oil bath, keeping 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 hour, then the reaction temperature was raised to 80 °C and it was allowed to continue until all hydride was consumed. After completion of the hydrosilylation polymerization, the unreacted starting material, volatile compounds and solvent were stripped under reduced pressure. The final product was obtained as a yellow liquid in quantitative yield and decolored with activated charcoal to obtain the desired product as a colorless liquid in quantitative yield (viscosity at 25 °C: 6810 mPa-s; GPC: M n = 3.06 kD; M w = 4.6 kD; PDI = 1.5)

[0164]

[0165] A norbornene-terminated phenylmethylsiloxane norbornenylethyl block copolymer (component A-2) having a molecular weight of 140 kD was synthesized analogously to the method described for A-1 :

[0166] In short, in a 500 mL three-necked round-bottom flask, 150 mL of toluene and 5-vinylbicyclo[2.2.1]hept-2-ene (94 g, 0.78 mol) were added. To this solution, 0.225 g of Karstedt catalyst (15 ppm of 2 wt% Pt) were added. 3-Phenyl-1,1,3,3,5-pentamethyltrisiloxane (200 g, 0.74 mol) in a dropping funnel was added dropwise over 1 h at 50 °C to the reaction mixture. Subsequently, the reaction temperature was raised to 80 °C and left to continue until all hydride was consumed. After completion of the hydrosilylation polymerization, the unreacted starting material, volatile compounds and solvent were stripped off under reduced pressure. The final product was obtained as a yellow liquid in quantitative yield and decolorized with activated charcoal to obtain the desired product as a colorless liquid in quantitative yield (viscosity at 25 °C: 14200 mPa-s; GPC: M n = 5.2 kD; M w = 7.8 kD; PDI = 1.5)

[0167]

[0168] Example 2: Component (A-2)

[0169] A compound of the following formula is provided as component A-2.

[0170]

[0171] Examples 3-10: Curable compositions

[0172] Example 3

[0173] A curable silicone composition was prepared by mixing 43.85 parts by mass of Al, 41.5 parts by mass of polyisobutylene (Olissopal 1000), 0.025 parts by mass of platinum-vinylsiloxane complex as a curing catalyst, and 0.125 parts by mass of maleic acid diallyl ester as a reaction inhibitor. Subsequently, 14.5 parts by mass of polypheryl-idemethylhydrosiloxy)siloxane crosslinking agent was added to the resulting mixture. The composition was mixed well in a speed mixer until uniform distribution of the components was obtained. This composition was then poured into a mold formed by glass plates to produce a thickness of 1 mm, and then heated at 150°C for 2 hours to produce a cured product.

[0174] Example 4

[0175] A curable silicone composition was prepared by mixing 26.75 parts by mass of silicone component Al, 63.6 parts by mass of polyisobutylene (Olissopal 1000), 0.025 parts by mass of platinum-vinylsiloxane complex catalyst, and 0.125 parts by mass of maleic acid diallyl ester as a reaction inhibitor. Subsequently, 9.5 parts by mass of component polypheryl-idemethylhydrosiloxy)siloxane as a crosslinking agent was added to the resulting mixture. The entire composition was mixed well in a speed mixer until uniform distribution of the components was obtained. This composition was then poured into a mold formed by glass plates to produce a thickness of 1 mm, and then heated at 150°C for 2 hours to thereby produce a cured product.

[0176] Example 5

[0177] A curable silicone composition was prepared by mixing 33.5 parts by mass of Al, 60 parts by mass of polyisobutylene (Olissopal 1000), 0.025 parts by mass of platinum-vinylsiloxane complex catalyst, and 0.125 parts by mass of maleic acid diallyl ester as a reaction inhibitor. Subsequently, 6.35 parts by mass of component polypheryl-idemethylhydrosiloxy)siloxane as a crosslinking agent was added to the resulting mixture. The entire composition was mixed well in a speed mixer until uniform distribution of the components was obtained. This composition was then poured into a mold formed by glass plates to produce a thickness of 1 mm, and then heated at 150°C for 2 hours to thereby produce a cured product.

[0178] Example 6

[0179] A curable silicone composition was prepared by mixing 25.9 parts by mass of Al, 60 parts by mass of polyisobutylene (Olissopal 1000), 0.025 parts by mass of platinum-vinylsiloxane complex catalyst, and 0.125 parts by mass of maleic acid diallyl ester as a reaction inhibitor. Subsequently, 10.35 parts by mass of the component hydride-modified MQ resin (MQH-9) was added to the resulting mixture as a crosslinking agent. The entire composition was mixed well in a speed mixer until uniform distribution of the components was obtained. The composition was then poured into a mold formed by glass plates to produce a thickness of 1 mm, and then heated at 150°C for 2 hours, thereby producing a cured product.

[0180] Example 7

[0181] A curable silicone composition was prepared by mixing 29.9 parts by mass of copolymer A-2, 59.9 parts by mass of polyacrylate (Ebecryl 745), 5 parts by mass of isobornyl acrylate, and 5 parts by mass of 2-ethylhexyl acrylate. Subsequently, 0.2 parts by mass of a radiation-curable initiator was added to the resulting mixture. The entire composition was mixed well in a speed mixer until uniform distribution of the components was obtained. The composition was then poured into a mold and subjected to UV irradiation (metal halide, 3000 mJ / cm 2 ), to form a cured product having a thickness of 1 mm.

[0182] Example 8

[0183] A curable composition was prepared similarly to the composition described in Example 7, with the addition of 59.9 parts by mass of copolymer A-2, 29.9 parts by mass of polyacrylate (Ebecryl 745), 10 parts by mass of isobornyl acrylate, and 0.2 parts by mass of a radiation-curable initiator. By curing the composition under UV irradiation, a 1 mm cured sheet was obtained.

[0184] Example 9

[0185] A curable composition was prepared similarly to the composition described in Example 7, with the addition of 49.9 parts by mass of copolymer A-2, 9.9 parts by mass of polyacrylate (EM 221), 20 parts by mass of isobornyl acrylate, 20 parts by mass of 2-ethyl hexyl acrylate, and 0.2 parts by mass of a radiation-curable initiator. By curing the composition under UV irradiation as described previously in Example 8, a 1 mm cured sheet was obtained.

[0186] Example 10

[0187] A curable composition was prepared in a similar manner to the composition described in Example 4, with the addition of 39.9 parts by mass of copolymer A-2, 49.9 parts by mass of Cl, 10 parts by mass of isobornyl acrylate, and 0.2 parts by mass of a radiation curable initiator. A 1 mm cured sheet was obtained by curing the composition under UV irradiation as described previously in Example 8.

[0188] Performance Evaluation

[0189] The performance of the cured sheets (1 mm) obtained from the examples was evaluated by the following methods. The results are summarized in Table 1.

[0190] Table 1

[0191]

[0192]

[0193] The viscosity of the curable composition was measured at 25°C using a HAAKE RheoStress 600.

[0194] To obtain information on the external appearance, the cured sheets of each example were visually inspected.

[0195] The transparency of the cured sheets was measured by a spectrophotometer (Gretag Macbeth Color Eye 7000A Spectrophotometer).

[0196] The water vapor permeability (WVTR) of the cured products was evaluated by the following method JIS Z0208 using a permeation cup tester by Yasuda Seiki Seisakusho Co., Ltd.

[0197] Table 2

[0198]

[0199] As shown in Table 2, the cured products obtained from the curable compositions exhibit excellent properties. The products are colorless and transparent and have a high degree of flexibility. In addition, the products exhibit resistance to discoloration upon exposure to heat and light, indicating their suitability as encapsulants and barrier adhesives in optoelectronic applications.

[0200] The foregoing description discloses various non-limiting embodiments of a heater assembly. Modifications can be made by those skilled in the art and within the scope of the present application. The disclosed examples are merely illustrative and not intended to limit the scope of the present application or the subject matter set forth in the claims.

Claims

1. An addition-curable silicone composition comprising: (A) Organopolysiloxanes having the following formula: Where R 1 It is selected from C1-C20 divalent hydrocarbons, C4-C20 branched divalent hydrocarbons, or C4-C30 divalent organic groups containing cyclic hydrocarbon groups; R 2 It is a curable functional group independently selected from vinyl groups, vinyl-containing groups, monovalent groups of unsaturated hydrocarbons, and monovalent groups of unsaturated cyclic hydrocarbons; R 3 -R 14 Independently selected from hydrogen, C1-C10 monovalent hydrocarbon groups, C6-C20 monovalent aromatic groups and C4-C30 monovalent saturated or unsaturated cycloalkyl groups, and siloxy groups containing 1-20 silicon atoms; x and z are independently 1-30; y and w are independently 0-30; and n is 1-30; (B) An organosilicon-free organic material comprising reactive functional groups selected from olefinic unsaturated monomers, wherein the olefinic unsaturated monomers are selected from olefinic unsaturated acids, olefinic unsaturated anhydrides, acrylates, methacrylates, and acrylamides. Or a combination of two or more of them; (C) Optionally, the crosslinking agent, when R 2 When the group is a vinyl group, a vinyl-containing group, a monovalent group of an unsaturated hydrocarbon, or a monovalent group of an unsaturated cyclic hydrocarbon, the crosslinking agent contains at least one Si-H or SH group; and (D) Reaction promoter.

2. The addition-curable silicone composition of claim 1, wherein the silicone-free organic material (B) is selected from organic monomers containing olefinic functional groups, organic monomers containing acrylic functional groups, organic oligomers containing acrylic functional groups, or combinations of two or more thereof.

3. The addition-curable composition of claim 2, wherein the monomer is selected from polyisobutylene containing an alkenyl functional group.

4. The addition-curable composition of claim 3, wherein the polyisobutylene is selected from vinyl-terminated polyisobutylene.

5. The addition-curable composition of claim 1, wherein the silicone-free organic material (B) is an organic monomer containing an acrylic functional group, selected from alkyl acrylates, alkylene glycol acrylates, epoxy acrylates, alkoxylated epoxy acrylates, alkoxyalkyl acrylates, aryl acrylates, urethane acrylates, amination acrylates, or combinations of two or more thereof.

6. The addition-curable composition of claim 5, wherein the organic monomer comprising the acrylic functional group is selected from 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethyl-2-adamantane acrylate, 2-ethyl-2-adamantane methacrylate, 2-hydroxyethyl acrylate, 2-methyl-2-adamantane acrylate, 2-methyl-2-adamantane methacrylate, benzyl acrylate, cyclohexyl acrylate, di(ethylene glycol) ethyl ether acrylate, di(ethylene glycol) ethyl ether methacrylate, di(ethylene glycol) methyl ether methacrylate, dicyclofentanil acrylate, epoxy acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, hydroxypropyl acrylate, isobornyl acrylate, methyladamantane acrylate, neopentyl glycol benzoate acrylate Esters, 2-hydroxymethyl methacrylate, adamantane methacrylate, alkyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, epoxycyclohexyl methacrylate, ethylene glycol phenyl ether methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, methyladamantane methacrylate, methyl methacrylate, methylglycidyl methacrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, alkyl acrylate, 2-hydroxy acrylate, trimethoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-fluoroethyl acrylate, 4-fluoropropyl acrylate, and triethylsiloxyethyl acrylate, or combinations of two or more thereof.

7. The addition-curable silicone composition as described in claim 1 or 2, wherein R 1 The group is selected from divalent groups containing C4-C30 cyclic hydrocarbon groups, wherein the C4-C30 cyclic hydrocarbon groups are selected from cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1,1-divinylcyclohexyl, 1,3-divinylcyclohexyl, bicyclo[2.2.1]-2,5-divinylheptyl, 1,4-di-2-prop-1-enylcyclohexyl, 1,3-diisopropenylphenyl, spiro[5.5]-3,8- Divinylundecyl, 1,3-divinyladamantyl, vinylnorbornel, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecyl, pinyl, camphenyl, norpinyl, norbornel, spiro[2.2]pentyl, spiro[2.3]hexyl, spiro[2.4]heptyl, spiro[2.5]octyl, spiro[3.3]heptyl, spiro[3.4]octyl, spiro[3.5]nonyl, spiro[ 4.4] Nonyl, spiro[4.5] Decyl, spiro[5.5] Undecyl, bicyclo[1.1.0] Butyl, bicyclo[2.1.0] Pentyl, bicyclo[2.2.0] Hexyl, bicyclo[3.1.0] Hexyl, bicyclo[3.2.0] Heptyl, bicyclo[3.3.0] Octyl, bicyclo[4.1.0] Heptyl, bicyclo[4.2.0] Octyl, bicyclo[4.3.0] Nonyl, bicyclo[4.4]. [0] Decyl, bicyclic [1.1.1]pentyl, bicyclic [2.1.1]hexyl, bicyclic [2.2.1]heptyl, bicyclic [2.2.2]octyl, bicyclic [3.1.1]heptyl, bicyclic [3.2.1]octyl, bicyclic [3.2.2]nonyl, bicyclic [3.3.1]nonyl, bicyclic [3.3.2]decyl, bicyclic [3.3.3]undecyl, adamantyl, tricyclic [5.2.1.0] 2,6 ] decyl and tricyclic [4.3.1.1 2,5 Undecyl.

8. The addition-curable silicone composition as described in claim 1 or 2, wherein R 2 It is selected from C1-C20 hydrocarbon groups containing vinyl functional groups, monovalent C4-C20 branched hydrocarbon groups containing vinyl functional groups, or monovalent C4 to C30 cyclic hydrocarbon groups containing vinyl functional groups.

9. The addition-curable silicone composition as described in claim 1 or 2, wherein R 2 XR 16 - where X is a curable functional group selected from vinyl (CH2=CH2-) or unsaturated cyclic groups, and R 16 It is a bond or a C1-C20 divalent hydrocarbon group.

10. The addition-curable organosilicon composition of claim 9, wherein X is selected from 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, tricyclic [4.3.1.1 2,5 Undecene, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methyleneadamantane, dicyclopentadiene or (-)-β-furfural monovalent group, or 4-vinylcyclohexyl.

11. The addition-curable silicone composition of claim 1 or 2, further comprising (E) an inhibitor; and / or (F) one or more additives.

12. The addition-curable organosilicon composition of claim 11, comprising the crosslinking agent (C), wherein the crosslinking agent is selected from organosilicon-containing compounds, the organosilicon-containing compounds comprising at least one -SiH group, at least one -SH group, a vinyl-containing group, an unsaturated hydrocarbon, an unsaturated cyclic hydrocarbon, a hydroxyl group, an alkoxy group, an epoxy group, or a combination of two or more thereof.

13. The addition-curable silicone composition of claim 1 or 12, wherein the reaction promoter is selected from photoinitiators, thermal initiators, metal-containing catalysts, or combinations of two or more thereof.

14. The addition-curable organosilicon composition of claim 11, wherein the inhibitor is selected from olefinically unsaturated amides, aromatically unsaturated amides, alkynes, olefinically unsaturated isocyanates, olefin siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or isolated alkynes, hydroperoxides, ketones, sulfoxides, amines, phosphites, nitrites, diaziridine, or combinations of two or more thereof.

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

16. The addition-curable silicone composition of claim 15, wherein the adhesion promoter is selected from aminosilane, epoxysilane, isocyanurate silane, mercaptosilane, iminosilane, acid anhydride silane, carboxylic acid ester-functionalized siloxane, or a combination of two or more thereof.

17. The addition-curable silicone composition of claim 1 or 2, wherein the composition has a refractive index of 1.40 to 1.

60.

18. The addition-curable silicone composition of claim 17, wherein the composition has ≥95% transparency.

19. The addition-curable silicone composition of claim 1 or 2, wherein the composition has 10 -1 Up to 10g / m 2 • Water vapor permeability per day.

20. A cured article formed by curing an addition-curable silicone composition as described in any one of claims 1-19.

21. The cured article of claim 20, wherein the article has a refractive index of 1.40 to 1.60, a transparency of ≥95%, and a density of 10... -1 Up to 10g / m 2 • Daily water vapor permeability, or a combination of both or more thereof.

22. The cured article of claim 20, wherein the article is selected from sealants, optical waveguides, lenses, adhesive materials, adhesives, films or sheets, laminates of sheets, coatings, pressure-sensitive adhesives, and wound care patches.

23. The cured article of claim 20, wherein the article is selected from LED sealants, optical waveguides, optical lenses, optical adhesives, optical films or sheets, or laminates of films in electronic components or in combination with semiconductor devices.

24. A personal care composition comprising an addition-curable silicone composition as described in any one of claims 1-19.

25. The personal care composition of claim 24, wherein the personal care composition is selected from cosmetic formulations, sunscreens, shampoos, conditioners, lotions, or creams.

26. A method of forming a cured article, comprising subjecting an addition-curable silicone composition as described in any one of claims 1-19 to thermal and / or UV radiation conditions to cure the composition.

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