Hardened silicone-acrylate composition, conductive material prepared thereby, and related methods

Abstract

A curable composition is disclosed. The curable composition comprises (I) an epoxide-functional silicone-acrylate polymer, (II) an aminosiloxane, and (III) a conductive filler. The epoxide-functional silicone-acrylate polymer comprises acrylate-derived monomer units comprising a siloxane moiety, an epoxide-functional moiety, and optionally a hydrocarbyl moiety, and the aminosiloxane comprises an average of at least two amine functional groups per molecule. A method for preparing the curable composition and its cured product is also disclosed. A method for forming a composite article comprising a conductive layer having the curable composition is also disclosed. The method comprises disposing the curable composition on a substrate and curing the curable composition to provide a conductive layer on the substrate, thereby forming the composite article.

Description

Technical Field

[0001] (Cross - reference to related applications) This application claims the priority and all advantages of U.S. Provisional Patent Application No. 62 / 964,455, filed on January 22, 2020, the content of which is incorporated herein by reference.

[0002] The present disclosure generally relates to siloxane - functionalized polymers, and more specifically to compositions comprising curable silicone - functionalized acrylate polymers and cured products, and to composite materials prepared therefrom.

Background Art

[0003] Silicones are polymer materials used in many commercial applications, mainly because their advantages are more prominent than those of their carbon - based analogs. More precisely, silicones, also called polymeric siloxanes or polysiloxanes, have an inorganic silicon - oxygen backbone (... -Si - O - Si - O - Si - O -...), with organic side groups bonded to silicon atoms. These side groups can be used to link two or more of these backbones together. By varying the -Si - O - chain length, side groups, and cross - linking, silicones with a wide variety of properties and compositions can be synthesized, and in a silicone network structure, the consistency can vary from liquid to gel, rubber, and hard plastic.

[0004] Silicone and siloxane-based materials are known in the art and are utilized in numerous end uses and environments. The most common silicone materials are those based on the linear organopolysiloxane polydimethylsiloxane (PDMS), which is a silicone oil. Such organopolysiloxanes are utilized in many industrial, home care, and personal care formulations. The second largest group of silicone materials are those based on silicone resins formed from branched and cage oligosiloxanes. Unfortunately, the use of siloxane-based materials in certain applications, which can benefit from certain unique properties of organopolysiloxanes (e.g., low loss and stable light transmittance, thermal stability, and oxidative stability), has remained limited due to the weak mechanical properties of conventional silicone network structures, which can appear in materials having insufficient or unsuitable characteristics such as low tensile strength, low tear strength, etc. Further, conventional silicone network structures and carbon-based polymers are often incompatible and / or possess antagonistic properties with respect to each other.

Summary of the Invention

[0005] A curable composition (the "composition") is provided. The composition comprises (I) an epoxide-functional silicone-acrylate polymer (the "silicone-acrylate polymer"), (II) an aminosiloxane comprising on average at least two amine functional groups per molecule, and (III) a conductive filler. The silicone-acrylate polymer has the following general average unit formula (I),

[0006]

Chemical formula

[0007] Also provided are a method of preparing the composition and its cured product. The cured product includes a reaction product of a silicone-acrylate polymer and an aminosiloxane formed in the presence of a conductive filler.

[0008] Also provided are a method of forming a composite article comprising a conductive layer (the "forming method") and the composite article formed thereby. The forming method includes disposing the composition on a substrate and curing the composition to provide a conductive layer on the substrate, thereby forming the composite article.

DETAILED DESCRIPTION OF THE INVENTION

[0009] A curable composition (the "composition") is provided. The curable composition includes (I) an epoxide-functional silicone-acrylate polymer, (II) an aminosiloxane containing on average at least two amine functional groups per molecule, and (III) a conductive filler. In addition to components (I), (II), and (III) described in order below, the composition is not particularly limited. The composition may alternatively contain none of a carrier vehicle, additives, reactants, and / or adjuvants, or may contain one or more of such components as also described below. The composition can be utilized in connection with a variety of end-use applications, including those in the preparation of functional materials suitable for use in or as composite materials, formable optical elements, adhesives, and the like.

[0010] Component (I) of the composition is an epoxide-functional silicone-acrylate polymer (i.e., "silicone-acrylate polymer"). The silicone-acrylate polymer (I) generally contains two or more monomer units derived from acryloxy-functional monomers and can thus be characterized, defined, or otherwise referred to as an acrylate or acrylic polymer or copolymer. However, as described below and illustrated by the examples herein, the silicone-acrylate polymer (I) may contain functional groups unrelated to acrylate / acryloxy functional groups or monomers (e.g., other polymer moieties, end-capping groups, etc.), but nevertheless may still be described or referred to simply as an acrylate polymer as understood by those skilled in the art. The silicone-acrylate polymer (I) is epoxide-functional, i.e., it contains at least one epoxide functional group as understood in view of the following description, and can thus react with compounds containing epoxide-reactive functional groups such as amines, particularly aminosiloxane (II) (e.g., in a crosslinking reaction, etc.).

[0011] The silicone-acrylate polymer (I) has the following general average unit formula (I),

[0012]

Chemical formula

[0013] Regarding formula (I), as introduced above, Y 1 represents a siloxane moiety. Generally, the siloxane moiety Y 1 contains siloxane and is not particularly limited otherwise. As understood in the art, siloxanes contain organosilicon and / or inorganic silicon-oxygen-silicon groups (i.e., -Si-O-Si-) attached to silicon atoms with organic side groups. Thus, siloxanes can be represented by the general formula ([R f SiO (4-f) / 2 e ) g (R) 3-g Si-, where the subscript f is independently selected from 1, 2, and 3 in each part indicated by the subscript e, the subscript e is at least 1, the subscript g is 1, 2, or 3, and each R is independently selected from a hydrocarbyl group, an alkoxy group, and / or an aryloxy group and a siloxy group.

[0014] ​Suitable hydrocarbyl groups for R include monovalent hydrocarbon moieties and their derivatives and modifications, which can independently be substituted or unsubstituted, straight-chain, branched, cyclic, or combinations thereof, and can be saturated or unsaturated. For such hydrocarbyl groups, the term "unsubstituted" describes a hydrocarbon moiety composed of carbon and hydrogen atoms, i.e., without heteroatom substituents. The term "substituted" means that at least one hydrogen atom is substituted with an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a pendant or terminal substituent), or a carbon atom within the hydrocarbon chain / skeleton is substituted with an atom other than carbon (e.g., a heteroatom such as oxygen, sulfur, nitrogen, etc.) (i.e., as part of the chain / skeleton), or both, and describes a hydrocarbon moiety. Thus, suitable hydrocarbyl groups may include hydrocarbon moieties having one or more substituents within and / or on their carbon chain / skeleton (i.e., attached to and / or integral with it), such that the hydrocarbon moiety may include ethers, esters, etc. Straight-chain and branched hydrocarbon groups can independently be saturated or unsaturated, and if unsaturated, can be conjugated or non-conjugated. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic and include cycloalkyl groups, aryl groups, and heterocycles that can be aromatic, saturated, and non-aromatic and / or non-conjugated, etc. Examples of combinations of straight-chain and cyclic hydrocarbyl groups include aralkyl groups, arylalkyl groups, etc. General examples of hydrocarbon moieties suitable for use in or as hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, alkynyl groups, halocarbon groups, and the like, and their derivatives, modifications, and combinations. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, and the like (i.e., other straight-chain or branched saturated hydrocarbon groups having, for example, more than 6 carbon atoms).Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethylphenyl and the like, as well as their derivatives and modifications, which may overlap with alkaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethylphenyl, etc.). Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl group and the like, as well as their derivatives and modifications. General examples of halocarbon groups include halogenated alkyl groups (e.g., any of the above alkyl groups in which one or more hydrogen atoms are substituted with a halogen atom such as F or Cl), aryl groups (e.g., any of the above aryl groups in which one or more hydrogen atoms are substituted with a halogen atom such as F or Cl), and halogenated derivatives of the above hydrocarbon moieties such as combinations thereof. Examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl and the like, as well as their derivatives and modifications. Examples of halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl group and the like, as well as their derivatives and modifications.

[0015] Suitable alkoxy and aryloxy groups for R include those having the general formula -OR i wherein R iis one of the hydrocarbyl groups described above with respect to R. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, benzyloxy and the like, as well as their derivatives and modifications. Examples of aryloxy groups include phenoxy, tolyloxy, pentafluorophenoxy and the like, as well as their derivatives and modifications.

[0016] Examples of suitable siloxy groups for R include [M], [D], [T] and [Q] units, each representing a structural unit of an individual functional group present in a siloxane such as an organosiloxane and an organopolysiloxane, as understood in the art. More specifically, [M] is the general formula R ii 3SiO 1 / 2 represents a monofunctional unit, [D] is the general formula R ii 2SiO 2 / 2 represents a difunctional unit, and as shown by the following general structural moiety, [T] is the general formula R ii SiO 3 / 2 represents a trifunctional unit, and [Q] is the general formula SiO 4 / 2 represents a tetrafunctional unit:

[0017]

Chemical formula

[0018] In these general structural moieties, each R ii is independently a monovalent or polyvalent substituent. As understood in the art, the specific substituents suitable for each R ii are not limited and can be monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated and combinations thereof. Typically, each R ii is independently selected from a hydrocarbyl group, an alkoxy group and / or an aryloxy group and a siloxy group. Thus, each R ii is independently a hydrocarbyl group of the formula -R i or a group of the formula -OR i [wherein, R iis an alkoxy or aryloxy group as defined above (e.g., containing any of the hydrocarbyl groups described above for R), or a siloxy group represented by any one or combination of the above [M], [D], [T] and / or [Q] units.

[0019] Siloxane moiety Y 1 can be, for example, linear, branched, or a combination thereof, based on the number and arrangement of [M], [D], [T] and / or [Q] siloxy units present therein. When branched, the siloxane moiety Y 1 can be at least minimally branched, or alternatively, hyperbranched and / or dendritic.

[0020] In certain embodiments, the siloxane moiety Y 1 is a branched siloxane moiety having the general formula -Si(R 3 )3, wherein at least one R 3 is -OSi(R 5 )3, and each other R 3 is independently selected from R 4 and -OSi(R 5 )3. In such embodiments, each R 5 is independently selected from R 4 , -OSi(R 6 )3 and -[-D 2 -SiR 4 2] m OSiR 4 3, wherein each R 6 is independently selected from R 4 , -OSi(R 7 )3 and -[-D 2 -SiR 4 2] m OSiR 4 3, wherein each R 7 is independently selected from R 4 and -[-D 2 -SiR 4 2] m OSiR 4 3. In each selection, R 4is an independently selected substituted or unsubstituted hydrocarbyl group such as any of those described above with respect to R, D 2 is a divalent linking group individually selected in each moiety denoted by the subscript m, and each subscript m is individually selected such that 0 ≦ m ≦ 100 (i.e., in each selection where applicable).

[0021] Y 1 In such branched siloxane moieties, each divalent linking group D 2 is typically selected from oxygen (i.e., -O-) and divalent hydrocarbon groups. Examples of such hydrocarbon groups include the divalent forms of the above-described hydrocarbyl and hydrocarbon groups such as any of those described above with respect to R. Thus, it will be understood that the hydrocarbon groups suitable for the divalent linking group D 2 can be substituted or unsubstituted and linear, branched and / or cyclic. However, typically, when the divalent linking group D 2 is a divalent hydrocarbon group, D 2 is selected from unsubstituted linear alkylene groups such as ethylene, propylene, butylene and the like.

[0022] In certain embodiments, each divalent linking group D 2 is oxygen (i.e., -O-), and as a result, each R 5 is independently selected from R 4 , -OSi(R 6 )3 and -[OSiR 4 2] m OSiR 4 3, each R 6 is independently selected from R 4 , -OSi(R 7 )3 and -[OSiR 4 2] m OSiR 4 3, and R 7 is independently selected from R 4 and -[OSiR 4 2] m OSiR 4 3, wherein in the formula, each R 4is as defined and described above, and each subscript m is as defined above and as described below.

[0023] As introduced above, each R 3 is R 4 and -OSi(R 5 )3, provided that at least one R 3 is of the formula -OSi(R 5 )3. In certain embodiments, at least two R 3 are of the formula -OSi(R 5 )3. In a particular embodiment, each R 3 is of the formula -OSi(R 5 )3. The greater the number of R 5 that are -OSi(R 3 )3, the more the level of branching in the siloxane moiety Y 1 increases. For example, when each R 3 is -OSi(R 5 )3, the silicon atom to which each R 3 is attached is a [T] siloxy unit. Alternatively, when only two R 3 are of the formula -OSi(R 5 )3, the silicon atom to which each R 3 is attached is a [D] siloxy unit. Further, when any R 3 is of the formula -OSi(R 5 )3 and at least one of these R 5 is of the formula -OSi(R 6 )3, additional siloxane linkages and branching are present in the siloxane moiety Y 1 . This is also the case when any R 6 is of the formula -OSi(R 7 )3. Thus, it will be understood by those skilled in the art that each subsequent R 1 moiety in the siloxane moiety Y 5+n can impart further branching depending on its particular selection. For example, at least one R 5 is of the formula -OSi(R 6)3, where at least one of these R 6 can be of the formula -OSi(R 7 )3. Therefore, depending on the choice of each substituent, further branching attributed to the [T] and / or [Q] siloxy units can be present in the siloxane moiety Y 1 (i.e., in addition to these other substituents / portions described above).

[0024] Each R 5 is independently selected from R 4 , -OSi(R 6 )3 and -[-D 2 -SiR 4 2] m OSiR 4 3, where each R 4 , D 2 and R 6 are as defined and described above, and each subscript m is as defined above and as described below. For example, when D 2 is oxygen (i.e., -O-), R 5 is selected from R 4 , -OSi(R 6 )3 and -[OSiR 4 2] m OSiR 4 3, where 0 ≦ m ≦ 100. Depending on the choice of R 5 and R 6 , further branching can be present in the siloxane moiety Y 1 . For example, when each R 5 is R 4 , each -OSi(R 5 )3 moiety (i.e., each R 5 in the formula -OSi(R 3 )3) is a terminal [M] siloxy unit. In other words, when each R 3 is -OSi(R 5 )3 and each R 5 is R 4 , each R 3 can be written as -OSiR 4 3 (i.e., an [M] siloxy unit). In such embodiments, the siloxane moiety Y 1is the group D in formula (I) 1 contains a [T] siloxy unit bonded thereto, and this [T] siloxy unit is capped by three [M] siloxy units. Further, R 5 is of the formula -[-D 2 -SiR 4 2] m OSiR 4 3, and when D 2 is oxygen (i.e., -O-), the siloxane moiety Y 1 contains optional [D] siloxy units (i.e., these siloxy units in each moiety denoted by the subscript m) and [M] siloxy units (i.e., represented by OSiR 4 3). Thus, when each R 3 is of the formula -OSi(R 5 )3 and R 5 is of the formula -[-D 2 -SiR 4 2] m OSiR 4 3, and when each D 2 is oxygen (i.e., -O-), each R 3 contains a [Q] siloxy unit. More specifically, in such embodiments, each R 3 is of the formula -OSi([OSiR 3 2] 4 OSiR m 3)3 such that when each subscript m is 0, each R 4 is a [Q] siloxy unit end-capped by three [M] siloxy units. Similarly, when the subscript m is greater than 0, each R 3 contains a linear moiety (i.e., a diorganosiloxane moiety) having a degree of polymerization attributed to the subscript m.

[0025] As described above, each R 5 can also be of the formula -OSi(R 6 )3. In embodiments where one or more R 5 are of the formula -OSi(R 6 )3, depending on the selection of R 6 , further branching occurs in the siloxane moiety Y 1may exist therein. More specifically, each R 6 is R 4 , -OSi(R 7 )3 and -[-D 2 -SiR 4 2] m OSiR 4 3, where each R 7 is R 4 and -[-D 2 -SiR 4 2] m OSiR 4 3, where each subscript m is as defined above. For example, in some embodiments, each D 2 is oxygen (i.e., -O-), and as a result, each R 6 is R 4 , -OSi(R 7 )3 and -[OSiR 4 2] m OSiR 4 3, where each R 7 is R 4 and -[OSiR 4 2] m OSiR 4 3, where the subscript m is as defined above and as will be described below.

[0026] Y 1 As introduced above with respect to the branched siloxane moiety of, the subscript m is 0 to 100, alternatively 0 to 80, alternatively 0 to 60, alternatively 0 to 40, alternatively 0 to 20, alternatively 0 to 19, alternatively 0 to 18, alternatively 0 to 17, alternatively 0 to 16, alternatively 0 to 15, alternatively 0 to 14, alternatively 0 to 13, alternatively 0 to 12, alternatively 0 to 11, alternatively 0 to 10, alternatively 0 to 9, alternatively 0 to 8, alternatively 0 to 7, alternatively 0 to 6, alternatively 0 to 5, alternatively 0 to 4, alternatively 0 to 3, alternatively 0 to 2, alternatively 0 to 1 (including), and alternatively 0. In certain embodiments, each subscript m is 0, and as a result, the siloxane moiety Y 1 does not contain [D] siloxy units.

[0027] Importantly, R3 , R 4 , R 5 , R 6 and R 7 each is independently selected. Thus, the above description for each of these substituents is not meant to imply, nor to indicate, that each substituent is the same. Rather, any of the above descriptions regarding R 5 is, for example, for only one R 5 , or for any number of R 1 in the siloxane moiety Y 5 , and so on throughout. Additionally, different selections of R 3 , R 4 , R 5 , R 6 and R 7 can result in the same structure. For example, if a particular R 3 is -OSi(R 5 )3, where each R 5 is -OSi(R 6 )3, where each R 6 is R 4 , then that particular R 3 can be written as -OSi(OSiR 4 3)3. Similarly, if a particular R 3 is -OSi(R 5 )3, where each R 5 is -[-D 2 -SiR 4 2] m OSiR 4 3, and the subscript m is 0, then that particular R 3 can be written as -OSi(OSiR 4 3)3. As shown, these particular selections result in the same final structure for R 5 based on different selections for R 3 . For that purpose, any conditions on the final structure of the siloxane moiety Y 1 should be considered to be satisfied by alternative selections that result in the same structure required by the conditions.

[0028] In certain embodiments, each R 4 is an independently selected alkyl group. In some such embodiments, each R 4 is an independently selected alkyl group having from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 1 to 4, alternatively from 1 to 3, alternatively from 1 to 2 carbon atoms.

[0029] In certain embodiments, each R 4 is methyl and the siloxane moiety Y 1 has one of the following structures (i) - (iv):

[0030]

Chemical formula

[0031] In certain embodiments, the siloxane moiety Y 1 is a linear siloxane moiety having the following general formula,

[0032]

Chemical formula

[0033]

Chemical formula

[0034] Generally, for the linear siloxane moiety of Y 1 the subscript n is equivalent to the above subscript m and thus represents a value from 0 (inclusive) to 100. Similarly, the subscript n can be from 0 to 60, alternatively from 0 to 40, alternatively from 0 to 20, alternatively from 0 to 19, alternatively from 0 to 18, alternatively from 0 to 17, alternatively from 0 to 16, alternatively from 0 to 15, alternatively from 0 to 14, alternatively from 0 to 13, alternatively from 0 to 12, alternatively from 0 to 11, alternatively from 0 to 10, alternatively from 0 to 9, alternatively from 0 to 8, alternatively from 0 to 7, alternatively from 0 to 6, alternatively from 0 to 5, alternatively from 0 to 4, alternatively from 0 to 3, alternatively from 0 to 2, alternatively from 0 to 1, etc., and can be from 0 to 80, alternatively 0. In certain embodiments, the subscript n is 0, and as a result, the linear siloxane moiety Y 1 does not contain [D] siloxy units in the segment denoted by the subscript q (i.e., when q is 1). However, in other embodiments, the subscript q is 1 and the subscript n is ≧1, and as a result, the linear siloxane moiety Y 1 of segment 1 contains at least one [D] siloxy unit. For example, in such embodiments, the subscript n is from 1 to 100, such as from 5 to 100, alternatively from 5 to 90, alternatively from 5 to 80, alternatively from 5 to 70, alternatively from 7 to 70, etc., and as a result, the linear siloxane moiety Y 1 of the segment contains a number of [D] siloxy units within one of those ranges.

[0035] The subscript o is from 2 to 6, and as a result, the segment denoted by the subscript o is a C2 - C6 alkylene group such as an ethylene, propylene, butylene, pentylene or hexylene group. Similarly, the subscript r is from 0 to 9, and when r is ≧1, the segment denoted by the subscript r is any of those described above with respect to the subscript 0, or a C1 - C9 alkylene group such as a heptylene, octylene or nonylene group.

[0036] The subscript letters s and t represent the substitution of the terminal silicon atoms of the linear siloxane moiety Y 1 . Generally, at least one of the subscript letters s and t is > 0 (i.e., s + t > 0). For example, in certain embodiments, the subscript letter s is 1 and the subscript letter t is 0. In other embodiments, the subscript letter s is 0 and the subscript letter t is 2. In certain embodiments, for the above linear siloxane moiety Y 1 , the general formula is subject to the condition that when the subscript letter s is 1, the subscript letter t is 0, and when the subscript letter s is 0, the subscript letter t is 2.

[0037] In some embodiments, the subscript letter q is 0 and the subscript letter t is 2, and as a result, Y 1 is of the general formula:

[0038]

Chemical formula

[0039]

Chemical formula

[0040] In certain embodiments, subscript p is 0, subscript q is 1, subscript s is 1, subscript t is 0, and each R 4 is methyl, and as a result, Y 1 is of the formula:

[0041]

Chemical formula

[0042] In certain embodiments, subscript q is 1, subscript p is 1, subscript n is 1, and as a result, Y 1 is of the formula:

[0043]

Chemical formula

[0044]

Chemical formula

[0045] Furthermore, with respect to formula (I), as introduced above, each D 1 is an independently selected divalent linking group. D 1The divalent linking group suitable for [the relevant context] is not particularly limited. Typically, the divalent linking group D 1 is selected from divalent hydrocarbon groups. Examples of such hydrocarbon groups include the divalent forms of the hydrocarbyl and hydrocarbon groups described above, such as any of those described above with respect to R. Thus, it will be understood that the hydrocarbon groups suitable for the divalent linking group D 1 can be substituted or unsubstituted and can be linear, branched, and / or cyclic.

[0046] In some embodiments, the divalent linking group D 1 comprises or alternatively is a linear or branched hydrocarbon moiety such as a substituted or unsubstituted alkyl group, an alkylene group, etc. For example, in certain embodiments, the divalent linking group D 1 comprises or alternatively is a C1-C d hydrocarbon moiety such as a linear hydrocarbon moiety having the formula -(CH2) 18 -, where the subscript d is from 1 to 18. In some such embodiments, the subscript d is from 1 to 12, alternatively from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 2 to 6, alternatively from 2 to 4, etc., up to 1 to 16. In a particular embodiment, the subscript d is 3, and as a result, the divalent linking group D 1 comprises or alternatively is propylene (i.e., a chain of 3 carbon atoms). As will be understood by those skilled in the art, each unit represented by the subscript d is a methylene unit, and as a result, the linear hydrocarbon moiety may be defined as or alternatively referred to as an alkylene group. It will also be understood that each methylene group can independently be unsubstituted and unbranched, or substituted (e.g., a hydrogen atom is substituted with a non-hydrogen atom or group) and / or branched (e.g., a hydrogen atom is substituted with an alkyl group). In certain embodiments, the divalent linking group D 1 comprises or alternatively is an unsubstituted alkylene group.

[0047] In some embodiments, the divalent linking group D 1 comprises or alternatively is a substituted hydrocarbon moiety such as a substituted alkylene group. In such embodiments, the divalent linking group D 1may include a carbon backbone having at least 2 carbon atoms and at least 1 heteroatom (e.g., O, N, S, etc.), such that the backbone includes an ether moiety, an amine moiety, and the like. For example, in certain embodiments, the divalent linking group D 1 includes, or alternatively is, an amino-substituted hydrocarbon group (i.e., a hydrocarbon including a nitrogen-substituted carbon chain / skeleton). For example, in some such embodiments, the divalent linking group D 1 is of the formula -D 3 -N(R 4 )-D 3 - and is an amino-substituted hydrocarbon, wherein each D 3 is an independently selected divalent hydrocarbon group and R 4 is as defined above (i.e., a hydrocarbyl group such as an alkyl group (e.g., methyl, ethyl, etc.)). In certain embodiments, R 4 is methyl in the amino-substituted hydrocarbon of the preceding formula. Each D 3 typically includes an independently selected alkylene group such as any of those described above with respect to the divalent linking group D 1 . For example, in some embodiments, each D 3 is independently selected from alkylene groups having 1 to 8 carbon atoms, such as 2 to 8 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms. In certain embodiments, each D 3 is propylene (i.e., -(CH2)3-). However, it should be understood that one or both D 3 may be or include another divalent linking group (i.e., other than the alkylene groups described above). Further, each D 3 can be substituted or unsubstituted, straight-chain or branched, and various combinations thereof.

[0048] Continuing with respect to formula (I), as introduced above, X 1 represents an epoxide-functional moiety, i.e., a moiety including an epoxide group. The epoxide group is not particularly limited and may be any group including an epoxide (e.g., a 3-membered cyclic ether of 2 carbons). For example, X 1It may contain or be a cyclic epoxide or a linear epoxide. As will be understood by those skilled in the art, an epoxide (e.g., an epoxide group) is schematically described in terms of the carbon chain skeleton formed by two epoxide carbons (e.g., an epoxyalkane derived from the epoxidation of an alkene). For example, a linear epoxide generally contains a linear hydrocarbon containing two adjacent carbon atoms bonded to the same oxygen atom. Similarly, a cyclic epoxide generally contains a cyclic hydrocarbon containing two adjacent carbon atoms bonded to the same oxygen atom, and at least one, typically both, of the adjacent carbon atoms are in the ring of the cyclic structure (i.e., form part of both the epoxide ring and the hydrocarbon ring). The epoxide may be a terminal epoxide or an internal epoxide. X 1 Specific examples of epoxides suitable for 1 include epoxyalkyl groups (e.g., epoxyethyl group, epoxypropyl group (i.e., oxiranylmethyl group), oxiranylbutyl group, epoxyhexyl group, oxiranyloctyl group, etc.), epoxycycloalkyl groups (e.g., epoxycyclopentyl group, epoxycyclohexyl group, etc.), glycidyloxyalkyl groups (e.g., 3-glycidyloxypropyl group, 4-glycidyloxybutyl group, etc.) and the like. Those skilled in the art will understand that such epoxide groups can be substituted or unsubstituted.

[0049] In certain embodiments, X 1 is of the formula

[0050]

Chemical formula

[0051]

Chemical formula

[0052]

Chemical formula

[0053] Furthermore, with respect to formula (I), as introduced above, each R 1 is independently selected from H and CH3. In other words, R 1 is independently H or CH3 in each part denoted by subscript a, independently H or CH3 in each part denoted by subscript b, and independently H or CH3 in each part denoted by subscript c. In certain embodiments, R 1 is CH3 in each part denoted by subscript a. In these or other embodiments, R 1 is CH3 in each part denoted by subscript b. In these or other embodiments, R 1 is CH3 in each part denoted by subscript c. In certain embodiments, R 1 is CH3 in each part denoted by subscripts a and b, and R 1 is H in each part denoted by subscript c. However, it will be understood that the part denoted by subscripts a, b, and / or c may include a mixture of different R 1 groups. For example, in certain embodiments, R 1 is H in the majority of the parts denoted by subscript c, and R 1 is CH3 in the remaining parts denoted by subscript c.

[0054] Furthermore, with respect to formula (I), as introduced above, R 2 represents a substituted or unsubstituted hydrocarbyl group. Examples of such hydrocarbyl groups include those described above for R.

[0055] In some embodiments, each R 2 is a hydrocarbyl group having 1 to 20 carbon atoms. In certain such embodiments, R 2contains or alternatively is an alkyl group. Suitable alkyl groups include saturated alkyl groups which can be linear, branched, cyclic (e.g., monocyclic or polycyclic) or combinations thereof. Examples of such alkyl groups include those having the general formula C j H 2j-2k+1 wherein the subscript j is from 1 to 20 (i.e., the number of carbon atoms present in the alkyl group), the subscript k is the number of independent rings / ring loops, and at least one carbon atom indicated by the subscript j is bonded to the carboxylic acid oxygen bonded to R 2 in the above formula (I). Examples of linear and branched isomers of such alkyl groups (i.e., when the alkyl group does not contain a cyclic group such that the subscript k = 0) include those having the general formula C j H 2j+1 wherein the subscript j is as defined above, and at least one carbon atom indicated by the subscript j is bonded to the carboxylic acid oxygen shown as bonded to R 2 in the above formula (I). Examples of monocyclic alkyl groups include those having the general formula C j H 2j-1 wherein the subscript j is as defined above, and at least one carbon atom indicated by the subscript j is bonded to R 2is bonded to the carboxylic oxygen shown as being bonded. Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups, including their straight-chain, branched, and / or cyclic isomers. For example, the pentyl group includes n-pentyl (i.e., the straight-chain isomer) and cyclopentyl (i.e., the cyclic isomer), as well as isopentyl (i.e., 3-methylbutyl), neopentyl (i.e., 2,2-dimethylpropy), tert-pentyl (i.e., 2-methylbutan-2-yl), sec-pentyl (i.e., pentan-2-yl), sec-isopentyl (i.e., 3-methylbutan-2-yl), etc., 3-pentyl (i.e., pentan-3-yl), and active pentyl (i.e., 2-methylbutyl), etc., including branched isomers.

[0056] In certain embodiments, each R 2 is independently selected from alkyl groups having 1 to 12 carbon atoms, such as 1 to 8 carbon atoms, alternatively 2 to 8 carbon atoms, alternatively 2 to 6 carbon atoms. In such embodiments, each R 2 is typically selected from methyl, ethyl, propyl (e.g., n-propyl and iso-propyl groups), butyl (e.g., n-butyl, sec-butyl, iso-butyl, and tert-butyl groups), pentyl (e.g., those described above), hexyl, heptyl, etc., and the like, as well as their derivatives and / or modified products. Examples of such derivatives and / or modified products of such alkyl groups include their substituted versions. For example, R 2 may include or alternatively be a hydroxyethyl group, which will be understood to be a derivative and / or modified product of the ethyl group described above. Similarly, R 2may contain, alternatively be, an acetoacetoxyethyl group, which may also be understood to be a derivative and / or modification of the above-described ethyl group (e.g., as an acetoacetoxy-substituted ethyl group) and / or a derivative and / or modification of the above-described other hydrocarbyl groups (e.g., a hexyl group substituted with esters and ketones).

[0057] In certain embodiments, each R 2 is independently selected from ethyl, n-butyl, isobutyl, isobornyl, cyclohexyl, neopentyl, 2-ethylhexyl, hydroxyethyl and acetoacetoxyethyl groups. In certain embodiments, at least one R 2 is a butyl group (e.g., n-butyl).

[0058] The subscripts a, b, and c represent the number of monomer units shown in the above formula (I), where the silicone-acrylate polymer (I) comprises a portion represented by at least 1 subscript a (i.e., subscript a ≥ 1), a portion represented by at least 1 subscript b (i.e., subscript b ≥ 1), and optionally, a portion represented by 1 or more subscripts c (i.e., subscript c ≥ 0). In other words, generally, subscript a is at least 1, alternatively greater than 1, subscript b is at least 1, alternatively greater than 1, and subscript c is 0, 1, or greater than 1. In certain embodiments, subscript a has a value of 1 to 100, such as 1 to 80, alternatively 1 to 70, alternatively 1 to 60, alternatively 1 to 50, alternatively 1 to 40, alternatively 1 to 30, alternatively 1 to 25, alternatively 5 to 25, etc. In these or other embodiments, subscript b has a value of 1 to 100, such as 1 to 80, alternatively 1 to 70, alternatively 1 to 60, alternatively 1 to 50, alternatively 1 to 40, alternatively 1 to 30, alternatively 1 to 20, alternatively 1 to 10, etc. In certain embodiments, subscript b has a value of 2 to 30, such as 2 to 25, alternatively 2 to 20, alternatively 2 to 10, alternatively 2 to 5, etc. In specific embodiments, subscript c is 0. In other embodiments, subscript c ≥ 1. For example, in some such embodiments, subscript c has a value of 1 to 100, such as 1 to 80, alternatively 1 to 70, alternatively 1 to 60, alternatively 1 to 50, alternatively 1 to 40, alternatively 1 to 30, alternatively 1 to 20, alternatively 1 to 15, etc. In some embodiments, the silicone-acrylate polymer (I) has a degree of polymerization (DP) of 2 to 100, such as 2 to 50, alternatively 5 to 50, alternatively 10 to 50, etc.

[0059] In certain embodiments, the portion represented by subscript b (i.e., the monomer unit containing the epoxide functional group X 1 is at least 30% of the total number of monomer units in the silicone-acrylate polymer (I) (i.e., b ≥ [0.3 *(a + b + c)], or at least 30 mol% of the silicone - acrylate polymer (I). In certain embodiments, the silicone - acrylate polymer (I) is present in an amount of at least 35, alternatively at least 40, alternatively 40 - 60, alternatively 40 - 50 mol%, based on the total amount of monomer units a, b, and c, and contains the moiety represented by subscript b. In some embodiments, the silicone - acrylate polymer (I) contains the moiety represented by subscript b in an amount of 10 - 40 wt%, such as 10 - 30, alternatively 15 - 30 wt%, based on the total weight of the monomers utilized to prepare the silicone - acrylate polymer (I).

[0060] It will be understood that the moieties represented by subscripts a, b, and c are independently selected. Thus, for example, if subscript a is at least 2, the silicone - acrylate polymer may contain two or more moieties represented by subscript a (i.e., different selections of R 1 , D 1 and / or Y 1 which are different from each other). Similarly, if subscript b is at least 2, the silicone - acrylate polymer may contain two or more moieties represented by subscript b (i.e., different selections of R 1 and / or X 1 which are different from each other). Likewise, if subscript c is at least 2, the silicone - acrylate polymer may contain two or more moieties represented by subscript c (i.e., different selections of R 1 and / or R 2 which are different from each other). For example, in a particular embodiment, subscript c is 0, and the silicone - acrylate polymer (I) contains two or more moieties representing different subscripts a, which are different from each other by different selections of Y 1 , and as a result, the above formula (I) can be rewritten into the following general unit formula,

[0061]

Chemical formula

[0062] [Chemical formula] wherein each variable is as described above with respect to the same specific moiety of the siloxane moiety Y 1 . Those skilled in the art will understand that other combinations and variations within the silicone-acrylate polymer (I), i.e., with respect to the moieties indicated by the subscripts a, b, and c, are equally possible within the scope of the description and examples of this specification.

[0063] In certain embodiments, the silicone-acrylate polymer (I) has a weight average molecular weight (Mw) of at least 500 Da and less than 75,000 Da. For example, the silicone-acrylate polymer (I) can have an Mw of 500 to 70,000, alternatively 1000 to 70,000, alternatively 1000 to 60,000, alternatively 1000 to 50,000, alternatively 2000 to 50,000, alternatively 2500 to 50,000 Da. In certain embodiments, the silicone-acrylate polymer (I) has a number average molecular weight (Mn) of at least 500 Da and less than 7500 Da. For example, the silicone-acrylate polymer (I) can have an Mn of 500 to 70,000, alternatively 1000 to 70,000, alternatively 1000 to 60,000, alternatively 1000 to 50,000, alternatively 1000 to 40,000, alternatively 1000 to 35,000, alternatively 2000 to 35,000, alternatively 2500 to 35,000 Da. In certain embodiments, the silicone-acrylate polymer has a peak molecular weight (Mp) (i.e., the average molecular weight representing the mode of the molecular weight distribution) of 1000 to 50,000, alternatively 2000 to 45,000, alternatively 3000 to 45,000 Da. In certain embodiments, the silicone-acrylate polymer has a peak molecular weight (Mp) of 1000 to 20,000, such as 1000 to 15,000, alternatively 1000 to 10,000, alternatively 1000 to 5000 Da. The molecular weight of the silicone-acrylate polymer (I) can be readily determined by techniques known in the art via gel permeation chromatography (GPC) against polystyrene standards (e.g., using size exclusion chromatography (GPC / SEC)).

[0064] Generally, the composition comprises a silicone - acrylate polymer (I) in an amount of 5 - 25 wt% based on the total weight of the composition. In certain embodiments, the composition comprises a silicone - acrylate polymer (I) in an amount of 5 - 20 wt%, such as 5 - 19, alternatively 5 - 18, alternatively 6 - 18 wt%, alternatively 5 - 18 wt% etc., based on the total weight of components (I), (II) and (III) in the composition. In some embodiments, the composition comprises a silicone - acrylate polymer (I) in an amount of 5 - 20 wt%, such as 5 - 19, alternatively 5 - 18, alternatively 6 wt% - 18 wt% etc., based on the total weight of the composition.

[0065] As introduced above, component (II) of the composition is an aminosiloxane. Generally, the aminosiloxane (II) comprises an amine - functional polysiloxane having a silicone backbone and on average at least two amine - functional groups per molecule. The amine - functional groups can be located anywhere along the silicone backbone, such as at the terminal positions, pendant positions or both. The amine - functional groups react with the epoxide groups of the silicone - acrylate polymer (I) (i.e., the above - mentioned epoxide - functional moiety X 1is configured to react with what is present therein, and as a result, the silicone - acrylate polymer (I) and the aminosiloxane (II) can react together (e.g., in a cross - linking reaction) to prepare a cured / mesh - structured product therefrom. Except for the amine functional groups, the aminosiloxane (II) is not particularly limited, and as long as the aminosiloxane (II) contains on average at least two amine functional groups per molecule, such units can contain any combination of [M], [D], [T] and / or [Q] siloxy units as described above. The siloxy units of the aminosiloxane (II) can be combined in various ways, i.e., to form cyclic, linear, branched and / or resinous (e.g., three - dimensional network - structured) structures within the silicone backbone. Thus, the silicone backbone of the aminosiloxane (II) can be monomeric, polymeric, oligomeric, linear, branched, cyclic and / or resinous depending on the selection of [M], [D], [T] and / or [Q] units therein. Similarly, the aminosiloxane (II) itself can be linear, branched, partially branched, cyclic, resinous (i.e., having a three - dimensional network structure) or can contain a combination of different structures.

[0066] Generally, the aminosiloxane (II) has a completely simplified formula R 8 i SiO (4-i) / 2 and in the formula, each R 8 is independently selected from hydrocarbyl groups, alkoxy and / or aryloxy groups and amine groups, provided that in each molecule, on average at least two of the R 8 each contain an amine group, and the subscript i is selected such that 0 < i ≦ 3.5. In certain embodiments, the aminosiloxane (II) can have the general average unit formula [R 8 i SiO (4-i) / 2 h where the subscript h ≧ 1, and the subscript i is independently selected from 1, 2 and 3 in each part indicated by the subscript h, provided that h + i > 2, and each R 8 ​is independently selected from hydrocarbyl groups, alkoxy and / or aryloxy groups, siloxy groups and amine groups (i.e., any of those described above), provided that on average at least two Rs 8 is the amine group per molecule of the aminosiloxane (II).

[0067] R 8 Suitable hydrocarbyl groups, alkoxy groups and aryloxy groups for R are as described above for R 8 Suitable amine groups for R include any of the above-described hydrocarbyl or alkoxy groups substituted with a primary or secondary amine group (i.e., an epoxide-reactive amine group). In certain embodiments, each R 8 is independently selected from hydrocarbyl groups, alkoxyaryloxy groups and amine groups. In certain embodiments, each R 8 is independently selected from alkyl groups having 1 to 20 carbon atoms (e.g., methyl group, ethyl group and propyl groups (i.e., n-propyl group and isopropyl group)), aryl groups having 6 to 20 carbon atoms (e.g., phenyl group), halogenated alkyl groups having 1 to 20 carbon atoms (e.g., chloromethyl group, chloropropyl group and trifluoropropyl group) and amine groups. In certain embodiments, each R 8 that is not an amine group is a methyl group.

[0068] The above average unit formula for aminosiloxane (II) can alternatively be written as [R 8 3SiO 1 / 2 x [R 8 2SiO 2 / 2 y 8 SiO 3 / 2 z [SiO 4 / 2 w wherein R 8 ​​​​​are as defined above, and are molar fractions representing the [M], [D], [T], and [Q] units, respectively, such that x + y + z + w = 1, with the condition that the subscripted letters x, y, z, and w each satisfy x + y + z > 0. One skilled in the art will understand how such [M], [D], [T], and [Q] units and their molar fractions affect the subscripted letters x, y, z, and w in the average unit formula above. For example, the [T] unit (e.g., represented by the subscripted letter z) and / or the [Q] unit (e.g., represented by the subscripted letter w) are typically present in the amino-siloxane resin, whereas the amino-siloxane polymer (e.g., amino-silicone) typically does not contain such [T] units and / or [Q] units. The [D] unit represented by the subscripted letter x is typically present in both the amino-siloxane resin polymer. However, such [D] units can also be present in the amino-siloxane resin and the branched amino-siloxane. In certain embodiments, the amino-siloxane (II) substantially does not contain or alternatively does not contain the [Q] unit (e.g., in the formula, the subscripted letter w is 0), such that the amino-siloxane (II) has the following general formula, [R 8 3SiO 1 / 2 x [R 8 2SiO 2 / 2 y 8 SiO 3 / 2 z , wherein R 8 and the subscripted letters x, y, and z are as defined above.

[0069] In certain embodiments, the amino-siloxane (II) can be substantially linear or alternatively is linear. In such embodiments, the amino-siloxane (II) can have the simplified formula R 8 i SiO (4-i) / 2 , wherein each R 8 ​​​​is independently selected and as defined above, where the subscript i is selected such that 1.9 ≦ i ≦ 2.2. Such linear examples of the aminosiloxane (II) can exist as a fluid liquid under ambient conditions (e.g., at 25 °C), such as when the aminosiloxane (II) has a viscosity of 10 to 30,000,000 mPa·s, alternatively 100 to 1,000,000, alternatively 100 to 100,000 mPa·s, such as 10 to 10,000,000 mPa·s (e.g., as determined via a viscometer such as a Brookfield LV DV-E viscometer equipped with a suitable spindle) at 25 °C. In certain embodiments, the aminosiloxane (II) exhibits a dynamic viscosity of less than 300, alternatively less than 200, alternatively 10 to 200 centipoise (cP) at 25 °C.

[0070] In the case of being substantially linear or linear, the aminosiloxane (II) substantially does not contain or alternatively does not contain both [T] and [Q] units (e.g., in the above formula, when z = 0 and w = 0), and as a result, the aminosiloxane (II) is an MDM-type polysiloxane having the following general formula, [R 8 3SiO 1 / 2 x [R 8 2SiO 2 / 2 y , wherein each R 8 and the subscripts x and y are as defined above. Each of the units represented by the subscripts x and y is independently selected, and when at least two R 8 are amine groups per molecule of the aminosiloxane (II), the preceding formula is [R 10 R 9 2SiO 1 / 2 x’ [R 10 R 9 SiO 2 / 2 y’ [R 9 2SiO 3 / 2 y’’ [R 9 3SiO 1 / 2 x’’ ​​​​​​can be rewritten as follows, wherein each R 9 is an independently selected monovalent hydrocarbon group, each R 10 is an amino functional group, the subscripts x' and x'' are each independently 0, 1 or 2, the subscript y' is ≧0, the subscript y'' is ≧0, provided that x'x''≧2, x'+y'≧2 and y'+y''≧1. In such embodiments, x'+x''+y'+y'' is generally 3 to 2,000. For example, in some embodiments, the subscript y'' can be 0 to 1000, alternatively 1 to 500, alternatively 1 to 200. In these or other embodiments, the subscript y' is 2 to 500, alternatively 2 to 200, alternatively 2 to 100. In such embodiments, x' and x'' are each typically 0 to 10, such as 2 to 6.

[0071] R 9 Suitable monovalent hydrocarbon groups for are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, halogenated aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, and halogenated aralkyl groups having 7 to 12 carbon atoms, where alkyl, aryl and halogenated alkyl, aralkyl, etc. are as described and exemplified above. In some embodiments, each R 9 is an alkyl group. For example, in certain embodiments, each R 9 is independently methyl, ethyl or propyl. However, it will be understood that each R 9 can be selected to be the same as or different from any other R 9 in terms of the group represented by a particular R 9 . However, in some embodiments, each R 9 is a methyl group.

[0072] If the aminosiloxane (II) is substantially linear or alternatively linear, at least two amine functional groups can be bonded to silicon atoms at pendant positions, terminal positions, or both pendant and terminal positions. As a specific example, when each R 9 is methyl, the aminosiloxane (II) has only pendant amine functional groups and thus has an average unit formula [(CH3)3SiO 1 / 2 2[(CH3)R 10 SiO 2 / 2 y’ [(CH3)2SiO 2 / 2 y’’ wherein the subscripts y’ and y’’ are as defined above, provided that y’ ≧ 2, and each R 10 is an independently selected amine functional group as defined and described above. For this average unit formula, any methyl group can be substituted with a different monovalent hydrocarbon group (such as alkyl or aryl). Alternatively, the aminosiloxane (II) has only terminal amine functional groups and thus can have an average formula R 10 (CH3)2SiO[(CH3)2SiO] y’’ Si(CH3)2R 10 wherein the subscripts y’’ and R 10 are as defined above. For this average formula, if the aminosiloxane (II) can be defined or otherwise described as a dimethylpolysiloxane terminated with an amine functional group, any methyl group can be substituted with a different monovalent hydrocarbon group, and it should be understood that each R 10 can be any of the amine functional groups described herein. Alternatively, the aminosiloxane (II) has both terminal and pendant amine functional groups and thus can have an average unit formula [R 10 (CH3)2SiO 1 / 2 x’ [R 10 (CH3)SiO 2 / 2 y’ [(CH3)2SiO 2 / 2 y’’ wherein each of x’, y’, y’’, and R 10 is as defined above.​​​​​

[0073] For example, in the preceding average unit formula, R 10 the amine functional group of the amino siloxane (II) represented by can form an N-C bond with the oxiranyl carbon atom of the silicone-acrylate polymer (I) (i.e., the above-mentioned epoxy-functional moiety X 1 present therein), and is not particularly limited otherwise. R 10 Suitable amine functional groups for are exemplified by aminoalkyl groups, aminoaryl groups, aminoalkaryl groups, and aminoaralkyl groups that are directly bonded to a silicon atom of the siloxane backbone of the amino siloxane (II) or to oxygen bonded to such a silicon atom (such as an aminoalkoxy group, an aminoaryloxy group, etc.).

[0074] In certain embodiments, the amino siloxane (II) has the following general formula, [R 9 3SiO 1 / 2 x [(H2N-D 3 -)(R 9 )2SiO 1 / 2 x’ [R 9 2SiO 2 / 2 y [(H2N-D 3 -)(R 9 )SiO 2 / 2 y’ , each D 3 is a divalent linking group independently selected, and R 9 as well as the subscripts x, x', y, and y' are as defined above. Provided that 0 ≦ x + x' < 1, 0 < y + y' < 1, and x' + y' > 0 are conditions.

[0075] D 3 Suitable divalent linking groups for are not particularly limited. Typically, each divalent linking group D 3 is selected from divalent hydrocarbon groups such as any of those described above with respect to D 1 . Thus, the divalent linking group D 3 ​​​​It will be understood that the hydrocarbon groups suitable for may be substituted or unsubstituted and linear, branched and / or cyclic. Typically, each of the divalent linking groups D 3 comprises or is alternatively a substituted or unsubstituted straight or branched chain alkyl group. In certain embodiments, each divalent linking group D 3 includes or is alternatively an unsubstituted alkylene group. Examples of such alkylene groups include any of those described herein, such as straight chain alkylene groups having 1 to 12 carbon atoms, optionally substituted with oxygen atoms in the chain. For example, in certain embodiments, D 3 contains an oxygen atom bonded to a silicon atom of the silicone backbone of the aminosiloxane (II) (eg, one of the silicon atoms of the units denoted by subscripts x' and / or y' above).

[0076] In the various formulas above, for example, the amine group, each R 9 For each R that is not 8 With respect to the silicon-bonded substituents represented by the formula: 8 , R 9 etc.), phenyl content (i.e., the number or percentage of each R 8 , R 9It can be characterized in terms of a number or ratio (such as etc.). In certain embodiments, for example, the aminosiloxane (II) has a high methyl content, such as at least 90, alternatively at least 95, alternatively at least 98, alternatively at least 99, alternatively at least 99.5, alternatively at least 99.9, alternatively at least 99.99% methyl content based on the total number of silicon-bonded substituents that are not amine groups. In certain embodiments, the aminosiloxane (II) has a low phenyl content, such as less than 10, alternatively less than 5, alternatively less than 2, alternatively less than 1, alternatively less than 0.5, alternatively less than 0.1, alternatively less than 0.01% phenyl content based on the total number of silicon-bonded substituents that are not amine groups.

[0077] When the aminosiloxane (II) is a substantially linear polyorganosiloxane, the aminosiloxane (II) can be exemplified by dimethylpolysiloxane endblocked with amino-functional dimethylsiloxy groups at both molecular ends, methylphenylpolysiloxane endblocked with amino-functional dimethylsiloxy groups at both molecular ends, a copolymer of methylphenylsiloxane and dimethylsiloxane endblocked with amino-functional dimethylsiloxy groups at both molecular ends, a copolymer of dimethylsiloxane and diphenylsiloxane endblocked with amino-functional dimethylsiloxy groups at both molecular ends, a copolymer of dimethylsiloxane, methylphenylsiloxane and diphenylsiloxane endblocked with amino-functional dimethylsiloxy groups at both molecular ends, a copolymer of amino-functional methylsiloxane and methylphenylsiloxane endblocked with trimethylsiloxy groups at both molecular ends, a copolymer of amino-functional methylsiloxane and diphenylsiloxane endblocked with trimethylsiloxy groups at both molecular ends, and a copolymer of amino-functional methylsiloxane, methylphenylsiloxane and dimethylsiloxane endblocked with trimethylsiloxy groups at both molecular ends.

[0078] In certain embodiments, the amino siloxane (II) has a weight average molecular weight (Mw) of at least 500 Da and less than 5000 Da. For example, the amino siloxane (II) can have an Mw of 500 - 4000, alternatively 500 - 3500, alternatively 500 - 3000, alternatively 500 - 2500, alternatively 500 - 2000, alternatively 750 - 2000, alternatively 750 - 1500, alternatively 750 - 1250 Da. In certain embodiments, the amino siloxane (II) has a number average molecular weight (Mn) of at least 500 Da and less than 5000 Da. For example, the amino siloxane (II) can have an Mn of 500 - 4000, alternatively 500 - 3500, alternatively 500 - 3000, alternatively 500 - 2500, alternatively 500 - 2000, alternatively 750 - 2000, alternatively 750 - 1500, alternatively 750 - 1250 Da. In some embodiments, the amino siloxane (II) has a degree of polymerization (DP) of 2 - 100, such as 2 - 75, alternatively 2 - 50, alternatively 5 - 50, alternatively 5 - 25. In the above embodiments, the relatively low molecular weight range described for the amino siloxane (II) provides a composition with suitable fluidity without the need for any carrier vehicle / solvent, as will be described in more detail below. However, one of ordinary skill in the art will understand that such a carrier vehicle / solvent can also be utilized with such relatively low molecular weight amino siloxanes without departing from the scope of the present disclosure. For example, in certain embodiments, the composition can include a carrier vehicle that can be removed after curing the composition, for example, to shrink the volume of the cured product and change (e.g., increase) its electrical conductivity. Similarly, such a carrier vehicle / solvent can be utilized in combination with an amino siloxane having a molecular weight outside the range described above (e.g., above), which can also be suitable for use as the amino siloxane (II).

[0079] Generally, the composition comprises the amino siloxane (II) in an amount of 1 to 20% by weight, based on the total weight of the composition. In certain embodiments, the composition comprises the amino siloxane (II) in an amount of 1 to 15% by weight, such as 1 to 14, alternatively 2 to 14% by weight, based on the total weight of components (I), (II) and (III) in the composition. In some embodiments, the composition comprises the amino siloxane (II) in an amount of 1 to 15% by weight, such as 1 to 14, alternatively 2 to 14% by weight, based on the total weight of the composition.

[0080] As introduced above, the amine functional group of the amino siloxane (II) is configured to react with the epoxide group of the silicone - acrylate polymer (I) to prepare a cured / meshed product therefrom. More specifically, the silicone - acrylate polymer (I) and the amino siloxane (II) react with each other via a cross - linking reaction based on the ring - opening amine - epoxide reaction between the amine functional group of component (II) and the epoxide group in X 1 of component (I). As will be understood by those skilled in the art, the cross - linking reaction prepares an amino siloxane - silicone - acrylate copolymer (the "copolymer"), which can generally be described or otherwise shown as an amino siloxane cross - linked silicone - acrylate copolymer.

[0081] The relative amounts of components (I) and (II) utilized in the composition can vary, for example, based on the selected silicone - acrylate polymer (I) and / or aminosiloxane (II), the type of conductive filler (III) utilized, etc. In certain embodiments, an excess of one of components (I) and (II) (e.g., in moles and / or stoichiometrically) is utilized to maximize the cross - linking of the silicone - acrylate polymer (I) and / or to completely consume the aminosiloxane (II). Generally, the silicone - acrylate polymer (I) and aminosiloxane (II) are utilized in the composition in a molar ratio of 10:1 to 1:10, alternatively 8:1 to 1:8, alternatively 6:1 to 1:6, alternatively 4:1 to 1:4, alternatively 2:1 to 1:2, alternatively 1:1 (I):(II). However, it will be understood that ratios outside of the above - specified ranges can also be utilized. For example, in certain embodiments, the aminosiloxane (II) is utilized in an overall excess (e.g., in an amount of ≧5 - fold, alternatively ≧10 - fold, alternatively ≧15 - fold, alternatively ≧20 - fold of the stoichiometric amount of the cross - linkable groups of the silicone - acrylate polymer (I)) when the aminosiloxane (II) is utilized as a carrier (i.e., solvent, diluent, etc.) for subsequent removal, for example. In any case, one of ordinary skill in the art will readily select the specific amounts and ratios of the various components, including the theoretical maximum reactivity ratios described above, the presence or absence of any carrier vehicle, the specific components utilized, etc., to prepare the copolymers according to the embodiments described herein.

[0082] In certain embodiments, the silicone - acrylate polymer (I) and aminosiloxane (II) are utilized in a stoichiometric ratio of 10:1 to 1:10, alternatively 8:1 to 1:8, alternatively 6:1 to 1:6, alternatively 4:1 to 1:4, alternatively 2:1 to 1:2, alternatively 1:1, alternatively 1:0.8[X 1 :[NH], where [X 1 represents the epoxide moiety X 1 of the silicone - acrylate polymer (I), and [NH] represents the number of amine functional groups of the aminosiloxane (II) (i.e., the amine functionality R 8 in the numerous embodiments described above, R10 represents a number such as etc., which is generally at least 2. More specifically, as understood by those skilled in the art, the crosslinking of the silicone-acrylate polymer (I) with the aminosiloxane (II) is based on the crosslinkable group X present in the silicone-acrylate polymer (I) 1 occurs at the theoretically maximum value based on the number. In particular, referring to the general formula (I) of the above silicone-acrylate polymer (I), X 1 each epoxide-functional moiety indicated by can react with one of the amine functional groups of the aminosiloxane (II) which has an average of at least two per molecule, and as a result, in order to achieve a theoretically complete (i.e., maximum) crosslinking reaction, for two epoxide-functional moieties indicated by X of the silicone-acrylate polymer (I) 1 one molar equivalent of aminosiloxane (II) is required for each two. Similarly, the theoretically maximum stoichiometric ratio of the reaction of the silicone-acrylate polymer (I) with the aminosiloxane (II) is 1:1 [X 1 :[NH], that is, here, the molecule of aminosiloxane requires two amine groups to crosslink two molecules of the epoxide-functional moiety, and each of these requires one epoxide group to participate in the reaction.

[0083] In certain embodiments, the silicone-acrylate polymer (I) and the aminosiloxane (II) are used in a stoichiometric ratio of 0.75:1 to 2.5:1 [NH]:[X 1 , for example, 0.75:1 to 2.25:1, alternatively 0.75:1 to 2:1, alternatively 0.75:1 to 1.75:1, alternatively 0.75:1 to 1.5:1 [NH]:[X 1 . As understood in the art, the ratio [NH]:[X 1 can be referred to as the curing stoichiometry of the curable composition and can be defined as the molar ratio of the active amine hydrogens attributed to the aminosiloxane (II) and the epoxide groups of the silicone-acrylate polymer (I), respectively.

[0084] Generally, the specific silicone - acrylate polymer (I) and aminosiloxane (II) utilized in the composition are not limited except for the parameters and characteristics described herein. However, in certain embodiments, the silicone - acrylate polymer (I) and aminosiloxane (II) are selected taking each other into account, for example, based on the mutual compatibility of the components. For example, in some embodiments, the silicone - acrylate polymer (I) and aminosiloxane (II) are selected such that when combined, a transparent liquid is obtained. More specifically, in such embodiments, the aminosiloxane (II) is compatible or alternatively miscible with the silicone - acrylate polymer (I). In specific examples of these embodiments, the aminosiloxane (II) is compatible or alternatively miscible with the silicone - acrylate polymer (I) at room temperature. In other such embodiments, the transparent liquid form can be achieved by combining components (I) and (II) together and then heating this combination (e.g., to a gently elevated temperature such as from a temperature higher than room temperature to less than 150, alternatively less than 125, alternatively less than 100 °C), solubilizing components (I) and (II), and then cooling or otherwise bringing the composition back to room temperature to obtain a transparent liquid.

[0085] Component (III) of the composition is a conductive filler. The conductive filler (III) can be electrically conductive, thermally conductive, or both thermally and electrically conductive and is otherwise not particularly limited. General examples of conductive fillers include organic fillers, inorganic fillers, and combinations thereof, including treated fillers and materials containing fillers otherwise, which exhibit an electrical conductivity (K) and / or a thermal conductivity (K) (e.g., an electrical conductivity (K) greater than 1×10 6 S / m and / or a volume resistivity (ρ) less than 0.001 ohm - cm at 20 °C) under the conditions described herein. As used herein, the volume resistivity (ρ) and electrical conductivity (K) refer to the bulk volume resistivity and bulk electrical conductivity. If the volume resistivity and conductivity are inconsistent for any reason, the volume resistivity is adjusted.

[0086] Some examples of suitable conductive fillers include pure metals (e.g., bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, metallic silicon, etc.), alloys (e.g., containing at least two metals such as bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, metallic silicon, etc.), metal oxides (e.g., alumina, zinc oxide, silicon oxide, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, barium titanate, zirconium oxide, strontium titanate, cerium oxide, cobalt oxide, indium tin oxide, hafnium oxide, yttrium oxide, tin oxide, niobium oxide, iron oxide, etc.), metal hydroxides, metal nitrides (e.g., boron nitride, aluminum nitride, silicon nitride, etc.), metal carbides (e.g., silicon carbide, boron carbide, titanium carbide, etc.), metal silicides (e.g., magnesium silicide, titanium silicide, zirconium silicide, tantalum silicide, niobium silicide, chromium silicide, tungsten silicide, molybdenum silicide, etc.), carbon (e.g., diamond, graphite, fullerene, carbon nanotube, graphene, activated carbon, and monolithic carbon black), soft magnetic alloys (e.g., Fe-Si alloy, Fe-Al alloy, Fe-Si-Al alloy, Fe-Si-Cr alloy, Fe-Ni alloy, Fe-Ni-Co alloy, Fe-Ni-Mo alloy, Fe-Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy, Fe-Si-Co-B alloy, etc.), ferrites (Mn-Zn ferrite, Mn-Mg-Zn ferrite, Mg-Cu-Zn ferrite, Ni-Zn ferrite, Ni-Cu-Zn ferrite, Cu-Zn ferrite, etc.) and the like, and those containing one or more components selected from combinations thereof.

[0087] Examples of electrically conductive fillers include, in particular, generally those containing a metal or a conductive non-metal, and particulate fillers having a particle core (e.g., polymers such as copper, solid glass, hollow glass, mica, nickel, ceramic fibers, polystyrene, polystyrene, polymethyl methacrylate, etc.) and a metal (e.g., precious metals such as silver, gold, platinum, palladium and their alloys, or base metals such as nickel, aluminum, copper or steel) or other electrically conductive materials (e.g., graphene) on the outer surface. Examples of thermally conductive fillers include, in particular, generally aluminum, copper, gold, nickel, silver, alumina, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, zinc oxide, barium titanate, diamond, graphite, carbon or silicon nano-sized particles, boron nitride, aluminum nitride, boron carbide, titanium carbide, silicon carbide and tungsten carbide.

[0088] The conductive filler (III) may include, or alternatively be, an inorganic filler. Examples of inorganic fillers include titanium dioxide, aluminum trihydroxide (“ATH”), magnesium dihydroxide, mica, kaolin, calcium carbonate, sodium, potassium, magnesium, calcium, and barium non-hydrated, partially hydrated, or hydrated fluorides, chlorides, bromides, iodides, chromates, carbonates, hydroxides, phosphates, hydrogen phosphates, nitrates, oxides, and sulfates, zinc oxide, aluminum oxide, antimony pentoxide, antimony trioxide, beryllium oxide, chromium oxide, iron oxide, lithopone, boric acid or borates, such as zinc borate, barium metaborate or aluminum borate, mixed metal oxides, such as aluminosilicates, vermiculite, fumed silica, fused silica, precipitated silica, quartz, sand, and silica including silica gel, rice husk ash, ceramics and glass beads, zeolite, metals such as aluminum flakes or powder, bronze powder, copper, gold, molybdenum, nickel, silver powder or flakes, stainless steel powder, tungsten, calcium silicate hydrate, barium titanate, silica-carbon black composites, functionalized carbon nanotubes, cement, fly ash, slate powder, ceramics or glass beads, bentonite, clay, talc, anthracite, apatite, attapulgite, boron nitride, cristobalite, diatomaceous earth, dolomite, ferrite, feldspar, graphite, calcined kaolin, molybdenum disulfide, perlite, pumice, pyrophyllite, sepiolite, zinc stannate, zinc sulfide or wollastonite and the like, and derivatives, modified forms, and combinations thereof. The conductive filler (III) may include, or alternatively be, a dielectric filler. Examples of dielectric fillers include ferroelectric fillers, paraelectric fillers, and combinations thereof, which can impart a relatively high dielectric constant so that the composition can store charge.Examples of these dielectric fillers include lead zirconate titanate, barium titanate, calcium metaniobate, bismuth metaniobate, iron metaniobate, lanthanum metaniobate, lead metaniobate, lead metatantalate, barium strontium titanate, sodium barium niobate, potassium barium niobate, rubidium barium niobate, titanium oxide, tantalum oxide, hafnium oxide, niobium oxide, aluminum oxide, and steatite.

[0089] The conductive filler (III) can include one or more of the above-described fillers in any form, such as a particulate form. Such particles are generally not limited and can independently be in the shape of a cube, flake, granule, irregular, rod, needle, powder, sphere, or a combination thereof. In certain embodiments, the conductive filler (III) includes particles having a maximum particle size of 500 μm, alternatively 200 μm, alternatively 100 μm, alternatively 50 μm, alternatively 30 μm. In these or other embodiments, the conductive filler (III) includes particles having a minimum particle size of 0.0001 μm, alternatively 0.0005 μm, alternatively 0.001 μm. In certain embodiments, the conductive filler (III) includes particles having a median particle size of 0.005 - 20 μm. In some embodiments, the conductive filler (III) includes particles having a median particle size of 0.005 - 100 μm, such as 0.005 - 50, alternatively 0.01 - 50 μm. The particle size can be determined by particle size distribution analysis and reported as the median particle size (D<50) in μm, alternatively as the diameter in μm at which a cumulative particle size distribution less than 10% (D10), 50% (D50), and 90% (D90) is found. The particles can have an aspect ratio in the range of 1:1 (substantially spherical) to 3,000:1.

[0090] The particles can be surface-treated to improve, for example, wettability (e.g., by other components of the composition) and / or dispersibility (e.g., in the composition). Examples of surface treatment generally include contacting the particles with chemical substances such as acids, bases, compatibilizers, lubricants, processing aids, etc., which can generally be referred to as "treatment agents" overall. Examples of such treatment agents are not limited and are exemplified by aqueous sodium hydroxide solution, carboxylic acids and esters (e.g., fatty acids, fatty esters, etc.), hydrocarbon vehicles, silicon-containing compounds (e.g., organochlorosilanes, organosiloxanes, organosilazanes, organoalkoxysilanes, etc.), sulfuric acid, etc. Examples of silicon-containing compound treatment agents include the same and combinations thereof.

[0091] In certain embodiments, the conductive filler (III) includes silver particles such as silver flakes, silver-coated core particles, or any other micronized solid form of silver. In some such embodiments, the silver particles include at least 90 atomic percent (%) Ag, e.g., >95% Ag, alternatively >98% Ag, alternatively >99.99% Ag. However, the silver particles can include much smaller amounts of silver, such as when silver-coated core particles are utilized. Such silver-coated core particles, and other coated core particles introduced above, can include a core that is a solid or liquid form of an internal support material. The internal support material can be a solid, or alternatively a liquid such as a liquid having a boiling point >300°C (e.g., mercury). In each coated core particle, the internal support material can be a single particle, alternatively a cluster or agglomerate of multiple particles. Generally, the internal support material is aluminum, silica glass, carbon, ceramic, copper, iron, lithium, molybdenum, nickel, organic polymer, palladium, platinum, silica, tin, tungsten, zinc, or an alloy of any two or more of aluminum, copper, iron, lithium, molybdenum, nickel, palladium, platinum, tin, tungsten, and zinc, or any two or more physical blends of metal alloys such as silica glass, carbon, ceramic, copper, iron, lithium, molybdenum, nickel, organic polymer, palladium, platinum, silica, tin, tungsten, zinc, or any of those described herein, or alternatively can be those. The internal support material can be electrically conductive or non-electrically conductive (insulating). The non-electrically conductive internal support material can be silica glass (e.g., soda lime silica glass or borosilicate glass), the polymorph diamond of carbon, silica, organic polymer, organosiloxane polymer, or ceramic.

[0092] Typically, the conductive filler (III) includes particles exhibiting a volume resistivity (ρ) of less than 0.01 ohm-cm. In certain embodiments, the conductive filler (III) has a volume resistivity in the range of less than 0.01 to 1.2×10 -2It contains particles showing a volume resistivity (ρ) of ohm-cm. In certain embodiments, the conductive filler (III) is 1.2×10 -2 less than ~ 1.2×10 -4 It contains particles containing particles showing a volume resistivity (ρ) of ohm-cm.

[0093] In some embodiments, the conductive filler (III) is 1×10 5 super, alternatively 1×10 6 It contains particles showing an electrical conductivity (K) of more than 1×10 4 S / m, alternatively more than 1×10

[0094] Generally, the conductive filler (III) constitutes more than half of the composition by weight, that is, it is present in the composition in an amount of at least 50% by weight based on the weight of the composition. In certain embodiments, the composition contains the conductive filler (III) in an amount of 60 - 83, alternatively 70 - 83, alternatively 75 - 83, alternatively 80% by weight, such as 60 - 83% by weight based on the total weight of the composition. In certain embodiments, the composition contains the conductive filler (III) in an amount of 60 - 83, alternatively 70 - 83, alternatively 75 - 83, alternatively 80% by weight based on the total weight of the components (I), (II) and (III) of the composition.

[0095] In certain embodiments, the composition further comprises one or more additional components such as one or more additives (e.g., agents, adjuvants, formulation ingredients, modifiers, auxiliary components, etc.) excluding components (I), (II), and (III). Typically, the composition may contain any number of additives, depending, for example, on the particular type and / or function in the composition. For example, in certain embodiments, the composition comprises a carrier, a filler other than component (III), a filler treatment agent, a surface modifier, a surfactant, a rheology modifier, a viscosity modifier, a binder, a thickener, a tackifier, an adhesion promoter, an antifoaming agent, a compatibilizer, a bulking agent, a plasticizer, a terminal blocking agent, a reaction inhibitor, a desiccant, a water releasing agent, a colorant (e.g., pigment, dye, etc.), a degradation preventing additive, a biocide, a flame retardant, a corrosion inhibitor, a catalyst inhibitor, a UV absorber, an antioxidant, a light stabilizer, a catalyst, a precatalyst or a catalyst generator, an initiator (e.g., a thermally activated initiator, an electro-magnetically activated initiator, etc.), a photoacid generator, a heat stabilizer and the like, and derivatives, modified products and combinations thereof, alternatively consisting essentially of them, alternatively consisting of one or more additives. Additives suitable for use in the composition can be classified into many different technical terms, and it should be understood that just because an additive is classified into such terms does not mean that it is limited to that function. Further, some of the additives may be present in a particular component of the composition (e.g., in the case of a multi-component composition) or alternatively incorporated when forming the composition instead.

[0096] In some embodiments, for example, the composition comprises a carrier vehicle. The carrier vehicle is not limited and is typically selected for the desired end use of the composition, etc., based on the particular silicone-acrylate polymer (I), aminosiloxane (II) and / or conductive filler selected. Generally, the carrier vehicle alternatively comprises, or alternatively consists of, a solvent, a fluid, an oil (e.g., an organic oil and / or a silicone oil), etc., or combinations thereof.

[0097] In some embodiments, the carrier vehicle comprises a silicone fluid. The silicone fluid is typically a low viscosity and / or volatile siloxane. In some embodiments, the silicone fluid is a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methyl ethyl siloxane and the like, or combinations thereof. Typically, the silicone fluid has a viscosity in the range of 1 to 1,000 mm 2 / s at 25°C. Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3, bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, and polydimethylsiloxane, polyethylsiloxane, polymethyl ethyl siloxane, polymethyl phenyl siloxane, polydiphenyl siloxane, caprylyl methicone, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone and the like, and their derivatives, modified products, and combinations thereof. Further examples of suitable silicone fluids include polyorganosiloxanes having a suitable vapor pressure such as 5×10 -7 ~1.5×10 -6 m 2 / s.

[0098] In certain embodiments, the carrier vehicle comprises an organic fluid typically comprising an organic oil comprising a volatile and / or semi-volatile hydrocarbon, ester and / or ether. General examples of such organic fluids include C6-C 16 alkanes, C8-C 16 isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8-C 16Volatile hydrocarbon oils such as branched esters (e.g., isodecyl neopentanoate, isodecyl neopentanoate, etc.) and the like, as well as their derivatives, modified products and combinations. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having 4 or more carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, acetates, alkyl halides, aromatic halides and combinations thereof. Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 ~C 13 ), Isopar H (C 11 ~C 12 ), and hydrogenated polydecene. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tripentacyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, dicaprylic acid / dicaprylic acid propylene glycol, octyl ether, octyl palmitate and combinations thereof.

[0099] In some embodiments, the carrier vehicle comprises an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and n-propanol; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol methyl ether acetate; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, white spirit, mineral spirit, naphtha, n-methylpyrrolidone, and the like, and derivatives, modified products, and combinations thereof. In certain embodiments, the carrier vehicle comprises a polar organic solvent such as a solvent that is miscible with water. Specific examples of such polar organic solvents utilized in specific embodiments include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-butanone, tetrahydrofuran, acetone, and combinations thereof.

[0100] Other carrier vehicles can also be used. For example, in some embodiments, the carrier vehicle includes an ionic liquid. Examples of ionic liquids include combinations of anions and cations. Generally, the anion is selected from alkyl sulfate-based anions, tosylate anions, sulfonic acid-based anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, hexafluorophosphate anions, tetrafluoroborate anions, and the like, and the cation is selected from imidazolium-based cations, pyrrolidinium-based cations, pyridinium-based cations, lithium cations, and the like. However, combinations of multiple cations and anions can also be used. Specific examples of ionic liquids typically include 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis-(trifluoromethanesulfonyl)imide, 3-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, N-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium, bis(trifluoromethanesulfonyl)imide, 1-allylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and the like, as well as their derivatives, modified products, and combinations.

[0101] In certain embodiments, the curable composition substantially does not contain or alternatively does not contain a carrier vehicle, except for components (I) and (II). In such embodiments, the silicone - acrylate polymer (I) and the aminosiloxane (II) are selected in consideration of each other such that the silicone - acrylate polymer (I) and the aminosiloxane (II) are miscible with each other.

[0102] In certain embodiments, the composition includes a filler in addition to compound (IIII). The additional filler is not limited and can be any filler that is compatible with the other components of the composition. Examples of such additional fillers include the conductive fillers described above and other fillers (e.g., non - conductive fillers). For example, reinforcing fillers, non - reinforcing fillers, or mixtures thereof can be utilized. Examples of reinforcing fillers include high - surface - area fumed silica and precipitated silica containing rice husk ash and micronized fillers such as a certain degree of calcium carbonate. Examples of non - reinforcing fillers include micronized fillers such as ground quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, carbon black, talc, and wollastonite. Other fillers that may be used alone or in addition to the above fillers include carbon nanotubes, e.g., multi - walled carbon nanotubes, aluminite, hollow glass spheres, calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesium carbonate, kaolin, aluminum trihydroxide, clays such as magnesium hydroxide (hydrotalcite), graphite, copper carbonate, e.g., malachite, nickel carbonate, e.g., zarachite, barium carbonate, e.g., witherite, and / or strontium carbonate, e.g., strontianite. Additional fillers suitable for use in the composition include silicates from the group consisting of the cancrinite family, the pectolite family, aluminosilicates, cyclic silicates, chain silicates, and layer silicates. In certain embodiments, several fillers can be utilized to adjust the thixotropic properties of the composition.

[0103] In various embodiments, the composition further comprises an adhesion promoter (e.g., an adhesion accelerator). The adhesion promoter can improve the adhesion of the reaction product formed from the curing of the composition (i.e., the copolymer formed through crosslinking of silicone-acrylate polymer (I) with aminosiloxane (II)) to the conductive filler (III), another component of the composition, and / or the base material contacted during curing. In certain embodiments, the adhesion promoter is selected from organosilicon compounds having at least one alkoxy group bonded to a silicon atom in the molecule. This alkoxy group is exemplified by a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. Further, the non-alkoxy groups bonded to the silicon atom of this organosilicon compound are, for example, substituted or unsubstituted monovalent hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a halogenated alkyl group and the like, an epoxy group-containing monovalent organic group such as a 3-glycidoxypropyl group, a 4-glycidoxybutyl group, or a similar glycidoxyalkyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, or a similar epoxycyclohexylalkyl group, and a 4-oxiranylbutyl group, an 8-oxiranyloctyl group, or a similar oxiranylalkyl group, an acrylic group-containing monovalent organic group such as a 3-methacryloxypropyl group and the like, and a hydrogen atom. The organosilicon compound of the adhesion promoter generally contains a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom. Further, due to the ability to impart good adhesion to various types of base materials, the organosilicon compound of the adhesion promoter generally contains at least one epoxy group-containing monovalent organic group in the molecule. These types of organosilicon compounds are exemplified by organosilane compounds, organosiloxane oligomers, and alkyl silicates, as understood by those skilled in the art. The molecular structures of the organosiloxane oligomers and / or alkyl silicates are exemplified by a linear structure, a partially branched linear structure, a branched chain structure, a cyclic structure, and a network structure, where the linear structure, the branched chain structure, and the network structure are typical.Specific organosilicon compounds for use as or in adhesion promoters include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and the like, siloxane compounds having at least one silicon-bonded alkenyl group or silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group in the molecule, silane compounds or siloxane compounds having at least one silicon-bonded alkoxy group in the molecule, and mixtures of siloxane compounds having at least one silicon-bonded hydroxy group and at least one silicon-bonded alkenyl group in the molecule, as well as methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate.

[0104] In certain embodiments, the composition includes accelerators and / or plasticizers such as benzyl alcohol, salicylic acid, and / or tris-2,4,6-dimethylaminomethylphenol.

[0105] One or more of the additives may be present in any suitable weight percent (wt%) of the composition, such as in an amount of 0.01 wt% to 65 wt%, alternatively 0.05 to 35, alternatively 0.1 to 15, alternatively 0.5 to 5 wt%. In these or other embodiments, one or more of the additives may be present in the composition in an amount of 0.1 wt% or less, alternatively 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 wt% or more. Those skilled in the art can readily determine the suitable amount of a particular additive, for example, depending on the type of additive and the desired result.

[0106] In certain embodiments, the composition substantially does not contain, or alternatively does not contain, a reaction catalyst or accelerator (i.e., a compound that exhibits catalytic activity and / or accelerating activity with respect to the crosslinking reaction of components (I) and (II) or otherwise the curing of the composition) other than components (I) and (II). In these or other embodiments, the composition substantially does not contain, or alternatively does not contain, a carrier vehicle (i.e., other than components (I) and (II)) (e.g., when one or both of components (I) and (II) can act as a carrier vehicle). In these or other embodiments, the composition substantially does not contain, or alternatively does not contain, an electrically conductive filler other than component (III). In these or other embodiments, the composition substantially does not contain, or alternatively does not contain, a bleed inhibitor other than components (I), (II), and (III). In certain embodiments, the composition substantially does not contain, or alternatively does not contain, each of a reaction catalyst or accelerator, a carrier vehicle, an electrically conductive filler, and a bleed inhibitor other than components (I), (II), and (III) (e.g., when one of such components exhibits an activity similar to that of a reaction catalyst or accelerator, a carrier vehicle, a conductive filler, and / or a bleed inhibitor).

[0107] The composition can be prepared using any method generally known in the art for preparing curable compositions. Generally, the composition is prepared by combining components (I), (II), and (III) together, optionally with any additional components utilized. The components can be combined in any order, simultaneously or in any combination thereof (e.g., in various multi-component compositions that are ultimately combined with each other). Similarly, the composition can be prepared in a batch, semi-batch, semi-continuous or continuous process, unless otherwise specified herein. Typically, when combined, the components of the composition are homogenized, for example, via mixing, which can be carried out by any of a variety of techniques known in the art using any equipment suitable for mixing. Examples of suitable mixing techniques generally include sonication, dispersion mixing, planetary mixing, three-roll milling, etc. Examples of mixing equipment include agitation batch kettles, ribbon blenders, solution blenders, co-kneaders, twin rotor mixers, Banbury type mixers, mills, extruders, etc. for compositions of relatively high fluidity (low dynamic viscosity), which can be batch-type or continuous compounding-type equipment and can be utilized alone or in combination with one or more mixers of the same or different types.

[0108] Also provided is a cured product formed from the composition. Generally, the cured product is formed by curing the composition, i.e., by crosslinking the silicone - acrylate polymer (I) with the aminosiloxane (II) in the presence of the conductive filler (III). Thus, the crosslinking reaction can be characterized as a "curing" reaction, and the resulting composition (i.e., containing the copolymer and the conductive filler (III)) is the cured product of the composition or its components. Thus, the cured product can be referred to as a cured composite or simply a composite. One of ordinary skill in the art will readily understand that the structure, molecular composition, and physical properties of the copolymer, and thus the composite containing it, are affected by the specific components of the composition (i.e., the selected silicone - acrylate polymer (I), the selected aminosiloxane (II), and any optional components utilized). Further, the composite can be further defined as a conductive composite, an adhesive, etc., depending on the formulation of the composition and the curing conditions utilized to prepare the composite.

[0109] The specific method of curing the composition is not particularly limited and can include any method and / or technique of curing known to one of ordinary skill in the art that is compatible with the components of the composition described above. Examples of curing methods and / or techniques include photocuring, moisture curing, crosslinking, etc. Generally, curing the composition includes crosslinking the silicone - acrylate polymer (I) with the aminosiloxane (II) as described above. However, other curing methods and / or techniques can also be utilized in combination with the aforementioned crosslinking, for example, when the composition contains other curing - compatible functional groups.

[0110] In certain embodiments, curing the composition includes heating the composition at or to an elevated temperature, for example, to facilitate crosslinking of the silicone - acrylate polymer (I) with the aminosiloxane (II). The elevated temperature, which may alternatively be referred to as the curing temperature of the composition, will be selected and controlled depending on the particular silicone - acrylate polymer (I) and / or aminosiloxane (II) being reacted, the type, nature and amount of the conductive filler (III) present in the composition, the conditions under which curing is carried out (e.g., whether under ambient or controlled conditions, whether the composition is disposed on a substrate during curing, etc.). Thus, the curing temperature will be readily selected by one of ordinary skill in the art considering the reaction conditions and parameters selected and the description herein. The curing temperature is typically above ambient temperature (e.g., above 25°C) to 200°C, alternatively 25 to 180, alternatively 25 to 165, alternatively 25 to 150, alternatively 30 to 150, alternatively 50 to 150, alternatively 70 to 150, alternatively 85 to 150, alternatively 100 to 150, alternatively 120 to 150°C, etc., 23 to 200°C. In certain embodiments, the curing temperature is selected and / or controlled based on the boiling point of any one solvent or volatile diluent, such as when reflux conditions are utilized.

[0111] Generally, the curing rate of the composition (i.e., in the presence of component (III), at least components (I) and (II)) increases when i) the curing temperature increases, ii) the relative epoxy and / or amine group content increases (i.e., in the silicone - acrylate polymer (I) and / or aminosiloxane (II), respectively), and iii) when relatively / relatively less sterically hindered silicone - acrylate polymers (I) and / or aminosiloxanes (II) are utilized. In an exemplary embodiment, the curing time of the composition (i.e., the crosslinking time via visual inspection and / or rheometry monitoring) is <5 minutes to >10 days, depending on the curing temperature for the silicone - acrylate polymer (I) and aminosiloxane (II) and the particular selections.

[0112] In certain embodiments, the composition can be characterized as an adhesive composition and a cured product as the adhesive. Generally, the adhesive is conductive due to the conductive filler (III) utilized in the composition. Thus, the adhesive can be further defined as a conductive adhesive. Aspects of the various embodiments described above provide adhesives having improved performance characteristics, such as with respect to bleed, conductivity, adhesion, etc.

[0113] In certain embodiments, the adhesive exhibits a bleed rate of less than 20 μm / min. In some such embodiments, the adhesive exhibits a bleed rate of less than 15 μm / min, alternatively less than 12, alternatively less than 10, alternatively less than 8, alternatively less than 6, alternatively less than 5 μm / min. The bleed rate of the adhesive can be measured according to the bleed test method described and explained below.

[0114] In certain embodiments, the adhesive exhibits a volume resistivity (ρ) of less than 0.012 ohm-cm, alternatively less than 0.0012, alternatively less than 0.00012 ohm-cm. In certain embodiments, the adhesive exhibits a volume resistivity (ρ) of from 1.2×10 -2 less to 1.2×10 -4 ohm-cm. The volume resistivity of the adhesive can be measured according to the volume resistivity test method described and explained below.

[0115] In certain embodiments, the adhesive exhibits an adhesive strength of at least 0.4 MPa. For example, in some embodiments, the adhesive exhibits an adhesive strength of at least 0.5 MPa, such as at least 0.6, alternatively at least 0.7, alternatively at least 0.8, alternatively at least 0.9, alternatively at least 1 MPa. In certain embodiments, the adhesive exhibits an adhesive strength of 0.7 to 4 MPa. However, the adhesive can include any maximum adhesive strength, such as a maximum adhesiveness of 7 MPa, alternatively 6 MPa, alternatively 5 MPa. The adhesive strength of the adhesive can be measured according to the adhesive strength test methods described and explained below. It should be understood that the adhesive strength of the adhesive can vary, for example, among different substrates, curing conditions, etc. Thus, the above adhesive strength values and ranges are merely applicable to the properties of the adhesive for one particular use (e.g., when utilized with a particular metal substrate (such as Al, Ni-Cu, clad, etc.), or alternatively for any number of uses. For example, in certain embodiments, the adhesive does not include an adhesion promoter (i.e., excluding components (I), (II), and (III)) and exhibits an adhesive strength according to the above values and ranges. Thus, it will be understood that in embodiments where the adhesive includes an adhesion promoter, the adhesive can include an adhesive strength in the upper part of the above range or even exceeding such a range.

[0116] It should be understood that the properties described above for the adhesive are equally applicable to other forms of the composition and its cured product.

[0117] The composition can be utilized to prepare a composite article, i.e., an article comprising a cured product disposed on a substrate. For example, the composite article can be formed by disposing the composition on the substrate (e.g., as a pre-prepared curable composition or stepwise to prepare the curable composition in situ on the substrate), curing the composition to obtain a cured product on the substrate, thereby preparing the composite article. In this way, the composition is typically used to prepare a layer on a substrate, such as a conductive layer.

[0118] The composition can be disposed or dispensed onto a substrate in any suitable manner (e.g., via spray coating, brushing, drawdown, roll coating, etc.). Typically, the composition is applied in a wet form by wet coating techniques. In certain embodiments, the composition can be applied by one of the following techniques: i) spin coating, ii) brush coating, iii) drop coating, iv) spray coating, v) dip coating, vi) roll coating, vii) flow coating, viii) slot coating, ix) gravure coating, x) Mayer bar coating, xi) printing, or xi) a combination of any two or more of i) - x). Typically, disposing the composition onto a substrate results in a wet deposit on the substrate, which is then cured to obtain a composite article as a coated substrate comprising a layer / membrane of the cured product as a coating.

[0119] The composition can be disposed or otherwise applied onto a substrate in any amount. For example, the composition can be applied in an amount sufficient to achieve an apparent dry film thickness (DFT) of at least 1 mil, alternatively at least 2 mils, alternatively at least 2.5 mils, alternatively at least 3 mils, where 1 mil is equal to 1 / 1000 of an inch.

[0120] The composition can be cured on the substrate at room temperature or elevated temperature (e.g., the elevated temperature described above with respect to the curing method), such as in a forced air oven or other type of heat source. For example, the substrate can include an integral heat source (e.g., a hot plate). The cured product can be physically and / or chemically bonded to the substrate or, alternatively, separable from the substrate, depending on the particular substrate and components of the composition utilized.

[0121] The substrate of the composite article is not limited and can be any substrate on which the composition can be disposed. Examples of substrates generally include plastics (e.g., thermoplastics and / or thermosetting resins), silicones, wood, metals (e.g., aluminum, steel, galvanized sheet, tin-plated steel, etc.), concrete, glass, ceramics, composites, cellulose (e.g., kraft paper, polyethylene-coated kraft paper (i.e., PEK-coated paper), thermal paper, plain paper, etc.), cardboard, paperboard, primed or painted surfaces and the like, and combinations thereof. Specific examples of suitable plastic substrates generally include thermoplastics such as polyamides (PA) and / or thermosetting resins, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), liquid crystal polyester, polyolefins such as polyethylene (PE), polypropylene (PP), polybutylene, styrene resins, polyoxymethylene (POM), polycarbonate (PC), polymethylenemethacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), polyether sulfone, polyketone (PK), polyether ketone, polyvinyl alcohol (polyvinylalcohol, PVA), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), polyethernitrile (PEN), phenolic resin, phenoxy resin, cellulose such as triacetyl cellulose, diacetyl cellulose, and cellophane, fluorinated resins such as polytetrafluoroethylene, thermoplastic elastomers such as polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluoro type, and copolymers and combinations thereof. However, it should be understood that composite articles can also be prepared by utilizing substrates other than those listed above, for example, by coating and curing a composition on such other substrates.

[0122] In addition, the substrate can have a continuous or discontinuous shape, size, dimension, surface roughness, and / or other such characteristics. In some embodiments, the substrate can have a softening point temperature at or below a high temperature, such that curing the composition at the high temperature enhances the mechanical adhesion of the cured product to the substrate.

[0123] The substrate is exemplified by, for example, components of a functional device. The specific type and nature of the functional device are not particularly limited and can be any type of optical, electrical and / or electronic device, and as a result, the components can include devices that house waveguides, electrical circuits, electrodes, etc., and can also be used for them. Specific examples of functional devices include optical devices, optoelectronic devices, optomechanical devices, magneto-optical devices, electrical and / or electronic devices, electro-optical devices, mechanical devices, electromechanical devices including microelectromechanical systems, magnetic devices, optoelectromagnetic devices, magnetomechanical devices, thermal devices, thermomechanical devices, thermo-optical devices, thermoelectric devices and / or thermoelectronic devices, thermomagnetic devices and the like, as well as derivatives, modifications and combinations thereof. As will be understood by those skilled in the art, the cured product and / or composite article can also be a component of a functional device such as any of those described above.

[0124] The term "polymer" is used herein in the conventional sense to generally denote a compound containing repeating units (i.e., monomer units) that can be prepared by reacting (i.e., polymerizing) monomers, whether of the same type or different types from each other. Thus, the term "polymer" encompasses the terms "homopolymer", which denotes a polymer in which the term contains only one type of monomer unit, "interpolymer", which denotes a polymer in which the term contains two different types of monomer units, and "terpolymer", which denotes a polymer in which the term contains three different types of monomer units. The term "copolymer" is also used herein in the conventional sense to denote a polymer containing at least two different types of monomer units such that the term "copolymer" encompasses interpolymers, terpolymers, etc. Thus, the term "polymer" also encompasses all forms of copolymers, including random, block, coblock, etc.

[0125] Polymers often contain or are “made from” one or more specific monomers, are “formed from” or “derived from” specific monomers or monomer types, and are said to “contain” a specific monomer content or proportion of specific monomers. However, in this context, the term “monomer” is understood to refer to the monomer units of the polymer itself, i.e., the polymerization residues of the specific monomers used in preparing the polymer, or units that can be so prepared, and not to non-polymerized monomer species. Thus, as used herein, a polymer is generally said to have monomer units in polymerized form, each of which corresponds to a non-polymerized monomer (i.e., even if such a monomer was not used to prepare the specific monomer units shown, such as when oligomers are used to prepare a particular polymer).

[0126] In any of the polymers described above, without changing the characterization of the polymer itself, trace amounts of impurities can be incorporated into or otherwise present in the polymer structure, which is generally classified based on the average monomer unit formula (i.e., excluding trace impurities from, for example, catalyst residues, initiators, end-capping agents, etc., that can be present in and / or incorporated into the polymer).

[0127] It should be understood that the appended claims are not limited to the specific compounds, compositions, or methods described in and expressing the “mode for carrying out the invention” and may vary among specific embodiments within the scope of the appended claims. For any Markush group relied upon herein to describe a particular feature or aspect of various embodiments, different, special, and / or unexpected results may be obtained from each member of each Markush group independent of all other Markush members. Each element of a Markush group may be relied upon individually and / or in combination and may provide a basis appropriate for a particular embodiment within the scope of the appended claims.

[0128] The following examples showing embodiments of the present disclosure are intended to illustrate the present invention and are not intended to limit the present invention. Unless otherwise specified, all reactions are carried out under air, and all solvents, substrates and reagents are purchased from various commercial suppliers or otherwise obtained and used as received.

[0129] The following instruments and characterization procedures / parameters are used to determine various physical properties of the compounds and compositions prepared in the following examples.

[0130] Instruments "Speedmixer" is a FlackTek DAC 150 speed mixer.

[0131] Nuclear Magnetic Resonance (NMR) spectroscopy Nuclear Magnetic Resonance (NMR) analysis is performed on a Varian Unity INOVA 400 (400 MHz) spectrometer using a 10 mm tube without silicon and a suitable solvent (e.g., CDCl3). Chemical shifts for the spectra are referenced to the internal protium solvent resonance ( 1 H: CDCl3 29 Si: tetramethylsilane).

[0132] Gel Permeation Chromatography (GPC) Gel permeation chromatography (GPC) analysis is performed on an Agilent 1260 Infinity II chromatograph equipped with an Agilent refractive index detector, using GPC / SEC software and equipped with a PLgel 5μm Mixed-C column (300×7.5 mm, Polymer Laboratories) preceded by a PLgel 5μm guard column. The analysis is carried out using a tetrahydrofuran (THF) mobile phase at a flow rate of 1.0 mL / min apparent flow rate at 35 °C. The sample is dissolved in THF (5 mg / mL) and optionally filtered through a 0.2 μm PTFE syringe filter prior to injection. Calibration is performed using a narrow polystyrene (PS) standard ranging from 580 to 2,300,000 g / mol that fits a third-degree polynomial curve.

[0133] Dynamic Viscosity:DV Viscosity measurements are performed on an Anton-Paar Physica MCR 301 rheometer equipped with a 25 mm stainless steel cone-in-plate fixture (CP25, 1.988 inch cone angle with 104 μM truncation) at an operating temperature of 25 °C using the Expert flow curve steady state control method available in the attached software package (Rheoplus 32 V3.40). A shear rate sweep from 0.1 to 500 s -1 is performed and the values at a frequency of 10 radians / second are reported in centipoise (cP).

[0134] Bleed test method The measurement of bleed is performed using a Keycene VHX 2000 digital optical microscope with a magnification in the range of 20 times to 50 times according to the following bleed test method.

[0135] A 5 cm × 0.5 cm strip of the uncured composite material (sample) is screen printed onto the rough surface of a ground glass microscope slide (Fisher Scientific, 3 inches × 1 inch × 1 mm). The slide is immediately placed under a microscope and an image of the printed composite material is recorded. The composite material is left to stand at room temperature for 60 minutes and then another image is recorded. Some of the polymer material is then observed when separated from the composite, creating the appearance of a wet surface layer on the ground glass slide. Using the built-in measurement features of the microscope, the distance between the edge of the printed composite and the bleed front is measured 5 times for each side of the printed material and the values are averaged to obtain the bleed distance in μm. The bleed rate in μm / min is then determined by recording and sorting additional bleed distances over a period of time.

[0136] Volume Resistivity Test Method Volume resistivity analysis is performed using a 4-probe probe instrument (GP 4-TEST Pro; GP Solar, GmbH) equipped with a line resistance probe head according to the following volume resistivity test method:

[0137] An aliquot of the uncured composite material (sample) is deposited onto a 4-inch × 4-inch glass slide by screen printing through an aperture (5 mm × 60 mm × 0.25 mm) to give 5 mm × 60 mm (300 mm 2A uniform strip having an area of ) is formed. Then, the printed material is cured at 150 °C (curing time = material-dependent; 1 hour (comparative example) to 4 hours (example)) to obtain a conductive strip as a cured layer on the slide, and the thickness of the cured layer is determined using a micrometer (Ono Sokki digital indicator EG-225). The electrical resistance passing through a distance of 5 cm along the conductive strip is measured using a line resistance probe head, and the resistivity of the cured sample is calculated using the equation (ρ = R (WxT / L), where ρ (rho) is the volume resistivity in ohm cm, R is the resistance in ohm of the cured composite measured between two inner probe tips placed at 5 cm intervals, W is the width of the cured layer in cm, T is the thickness of the cured layer in cm, and L is the length of the cured layer between two inner probes in cm).

[0138] Adhesion strength test method, lap shear adhesion The adhesion of the sample is tested using a double shear test, where the measurement of the tensile strength is carried out on a tensile testing machine (Instron, model 5566) according to the following adhesion strength test method.

[0139] Shear panels (bare aluminum, Ni-Cu, Alclad) with dimensions of 0.040 inches × 1 inch × 3 inches are wiped clean with Kimwipes and isopropyl alcohol, placed in an oven at 150 °C for 10 minutes to ensure complete solvent evaporation, and then cooled to room temperature. The panels are grouped into 5 pairs, and the first panel of each pair is marked 1 inch from the end of the panel. An aliquot (sample, approximately 2 g) of the uncured composite material is applied to the first panel within a 1-inch area between the mark and the end of the panel where the marks are measured. A portion of glass beads (Potter’s Industries Inc.; maximum diameter of 0.0098 inches; approximately 10 mg) is applied on top of the composite to establish a bond line, and then the second panel of each pair is gently pressed on top of a portion of the corresponding first panel to form an assembly, which is held together in place using binder clips. The assembly is placed in an oven at 150 °C for 4 hours to cure the composite material, and then cooled to room temperature overnight. Then, using a 10 KN load cell, 60 psi clamp pressure, and a tensile speed of 2 inches / minute, the assembly is analyzed on a tensile testing machine, and the tensile strength measurements recorded for each of the 5 prepared shear joints are averaged to obtain the adhesion strength value (MPa).

[0140] The various components used in the examples are listed in Table 1 below.

[0141]

Table 1-1

Table 1-2

Table 1-3

Table 1-4

[0142] General Procedure 1: Preparation of Epoxide-Functionalized Silicone-Acrylate Polymers Toluene (20 g) is added to an oven-dried 500 mL four-neck round-bottom flask equipped with a stirring shaft, condenser, thermocouple port, addition port, and heating mantle. A mixture of an organosilicon monomer (M1, 87 g), glycidyl (meth)acrylate (GMA, 24 g), and n-dodecanethiol (CTA, 8 g) (collectively referred to as the "monomer blend") is prepared and divided into two plastic syringes equipped with a feeding line in the flask and a Luer lock connector connected to a syringe pump. Benzoyl peroxide (BPO, 4.04 g) and toluene (40 g) ("initiator blend") are added to another plastic syringe equipped with a feeding line in the flask and a Luer lock connector connected to a syringe pump. The flask is heated to reach the target temperature (110 °C) with stirring, and at this point, the feeding of the monomer blend is started (rate: 2.5 g / min, duration: 40 min). After a 5-minute delay, the feeding of the initiator blend is started (duration: 120 min), 1 The reaction is monitored via 1H NMR. After the completion of both feedings, the reaction mixture is maintained at the target temperature (110 °C) with stirring for 1 hour, then cooled to room temperature (about 23 °C) to obtain a reaction product containing an epoxide-functional silicone-acrylate polymer (SA-1), which is isolated via distillation and characterized according to the above procedure.

[0143] Preparation Examples 1 to 7: Epoxide-functional silicone-acrylate polymers Using various acryloxy-functional organosilicon compounds ((M1) to (M5)), silicone-acrylate polymers (SA-1) to (SA-7) are prepared according to the procedure described in General Procedure 1 above to obtain Preparation Examples 1 to 7. The specific components and parameters of Preparation Examples 1 to 7 are listed in Table 2 below. After preparation, the silicone-acrylate polymers (SA-1) to (SA-7) are characterized according to the above procedure, and the results are also listed in Table 2 below.

[0144]

Table 2

[0145] Comparative Examples 1 and 2 A dental cup of 20 g is filled with Conductive Filler 1 (16 g). Next, Polysiloxane 1 (3.64 g) is added, and using a spatula, the resulting composition is gently mixed by hand and then mixed via a speed mixer (2000 rpm, 20 seconds). Next, Crosslinking Agent 1 (0.15 g) is added, and the resulting composition is mixed via a speed mixer (2000 rpm, 20 seconds). Next, Pt Catalyst 1 (0.20 g, 10 ppm of Pt) is added, and the resulting composition is mixed via a speed mixer (2000 rpm, 20 seconds). Next, the composition is degassed in a vacuum chamber connected to a rotary vane pump (1 torr, about 5 minutes), and then gently sheared with a speed mixer (2000 rpm, 10 seconds) to obtain a homogeneous curable composition (Comparative Composition 1). The curable composition is screen-printed and then cured at 150°C for 1 hour to prepare a cured composite (Comparative Composite 1).

[0146] The above procedure is repeated using Crosslinking Agent 2 to obtain another homogeneous curable composition (Comparative Composition 2), which is screen-printed and then cured at 150°C for 1 hour to prepare another cured composite (Comparative Composite 2). The specific parameters of Examples 1 to 2 are listed in Table 3 below.

[0147] After preparation, Comparative Composites 1 and 2 are evaluated for resistivity, bleed, and adhesion strength according to the above procedure. The results of these evaluations are listed in Table 3 below.

[0148] [Table 3]

[0149] General Procedure 2: Preparation of Curable Material Silicone-acrylate polymer (SA-7, 2.95 g) and aminosiloxane (AS-1, 1.05 g) are combined in a 20 g dental cup to form a composition having a target epoxy:amine equivalent ratio (1:1), and this is mixed via a speed mixer (2000 rpm, 20 seconds) to form a homogeneous solution. Then, conductive filler 1 (16 g) is added to the dental cup, and using a spatula, the resulting composition is gently mixed by hand and then mixed twice via a speed mixer (2000 rpm, 20 seconds). Then, the composition is degassed in a vacuum chamber connected to a rotary vane pump (1 torr, about 5 minutes) and then gently sheared with a speed mixer (1000 rpm, 10 seconds) to obtain a homogeneous curable composition.

[0150] Examples 1 to 42: Curable compositions According to the procedure described in General Procedure 2 above, silicone-acrylate polymers (SA-1) to (SA-8) from Preparation Examples 1 to 8 as component (I), and aminosiloxane (AS-1) or (AS-2) as component (II), and one of conductive fillers 1 as component (III) are used, and components (I) and (II) are utilized at a specific epoxy:amine equivalent ratio to prepare curable compositions to obtain Examples 1 to 42. The specific components and parameters of Examples 1 to 42 are described in Tables 4 and 5 below.

[0151] [Table 4]

[0152] [Table 5]

[0153] After preparation, the compositions of Examples 1 to 42 were evaluated for resistivity and bleed according to the above procedures using the volume resistivity test method and the bleed test method, respectively. The results of these evaluations are described in Table 6 below.

[0154] [Table 6] Here, "n.d." indicates a value that was not determined.

[0155] According to the above procedure, the compositions of Examples 1 to 42 are evaluated for adhesiveness using an adhesion strength test method. The results of these evaluations are shown in Table 7 below.

[0156]

Table 7

[0157] As shown, a curable composition utilizing a branched silicone moiety and a silicone - acrylate polymer containing more than 30 mol% of GMA (e.g., 40 and 50%) and an aminosiloxane having a molecular weight of about 1000 to 3000 produces a cured product that has good conductivity (volume resistivity < 0.0012 ohm cm), bleeding that is excellent (< 5 μm / min) to moderate (< 15 μm / min), high adhesiveness (> 1 MPa) with one or more substrates, moderate adhesiveness (> 0.5 MPa) with all substrates tested, and no complete adhesion failure. A curable composition utilizing a linear silicone moiety and a silicone - acrylate polymer having more than 40 mol% of GMA in combination with an aminosiloxane having a molecular weight of about 1000 to 3000 produces a cured product that has good electrical conductivity (volume resistivity < 0.0012 ohm cm), while a similar composition using a silicone - acrylate polymer having 40% of GMA produces a cured product with appropriate electrical conductivity.

Claims

1. A curable composition comprising: (I) an epoxide-functional silicone-acrylate polymer having the following general unit formula: 【Chemical 1】 In the formula, each R １ is independently selected from H and CH ３ and each R ２ is an independently selected substituted or unsubstituted hydrocarbyl group, each D １ is a divalent linking group, each Y １ is an independently selected siloxane moiety, and the siloxane moiety contains at least one [T] siloxy unit and / or [Q] siloxy unit, each X １ is an independently selected epoxide-functional moiety, subscript a ≥ 1, subscript b ≥ 1, subscript c ≥ 0, and the units represented by subscripts a, b, and c can be in any order in the silicone-acrylate polymer, an epoxide-functional silicone-acrylate polymer, and (II) an aminosiloxane containing on average at least two amine functional groups per molecule; and (III) an electrically conductive filler.

2. In the epoxy-functional silicone-acrylate polymer (I), at least one siloxane moiety Y １ is a siloxane group having the general formula -Si(R ３ ), ３ wherein each R ３ is independently selected from R ４ and -OSi(R ５ ), ３ with the proviso that at least one R ３ is -OSi(R ５ ), ３ wherein each R ５ is independently selected from R ４ , -OSi(R ６ ), ３ and -[-D ２ -SiR ４ ２ ｍ OSiR ４ ３ wherein each R ６ is independently selected from R ４ , -OSi(R ７ ), ３ and -[-D ２ -SiR ４ ２ ｍ OSiR ４ ３ wherein each R ７ is independently selected from R ４ and -[-D ２ -SiR ４ ２ ｍ OSiR ４ ３ and 0 ≤ m ≤ 100, wherein D ２ is a divalent linking group, and wherein each R ４ is independently a substituted or unsubstituted hydrocarbyl group, the curable composition according to claim 1.​​​

3. In the epoxy-functional silicone-acrylate polymer (I), (i) R １ is CH ３ in each part indicated by the subscript a, (ii) R １ is CH ３ in each part indicated by the subscript b, (iii) R １ is H in each part indicated by the subscript c, (iv) each R ２ is butyl, (v) each X １ is of the formula 【Chemical 2】 The curable composition according to Claim 1 or 2, wherein the epoxide group of (I) is an epoxypropyl group, or (vi) the subscript b is at least 30% of the total units represented by the subscripts a, b, and c, or (vii) any combination of (i) to (vi).

4. The aminosiloxane (II) has the following general formula: [R ９ ３ SiO １／２ ｘ [(H ２ N-D ３ -)(R ９ ) ２ SiO １／２ ) ｘ’ [R ９ ２ SiO ２／２ ) ｙ [(H ２ N-D ３ -)(R ９ )SiO ２／２ ) ｙ’ ​ In the formula, each R ９ is an independently selected hydrocarbyl group, each D ３ is an independently selected divalent linking group, and the subscripts x, x', y, and y' are mole fractions such that x + x' + y + y' = 1, provided that 0 ≦ x + x' < 1, 0 < y + y' < 1, and x' + y' > 0. The curable composition according to any one of claims 1 to 3.

5. The electrically conductive filler (III) contains (i) silver-coated metal particles, (ii) silver-coated organic particles, (iii) silver flakes, (iv) has a median particle size of 0.005 to 100 μm, (v) has an electrical conductivity (K) of 1×10 ６ S / m, or (vi) is any combination of (i) to (v), the curable composition according to any one of claims 1 to 4.

6. The curable composition according to any one of Claims 1 to 5, comprising (i) 5 to 20% by weight of component (I), (ii) 2 to 15% by weight of component (II), (iii) 65 to 83% by weight of component (III), or (iv) any combination of (i) to (iii), based on the total weight of components (I), (II), and (III).

7. A cured product of the curable composition according to any one of Claims 1 to 6.

8. A method of forming a composite article comprising an electrically conductive layer, the method comprising: depositing the composition on a substrate; and optionally curing the composition via heating to provide a conductive layer on the substrate, thereby forming the composite article, wherein the composition is the curable composition according to any one of Claims 1 to 6.

9. A composite article formed according to the method of Claim 8.

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