Curable silicone-based gel composition, cured gel thereof, encapsulation agent, electronic article, and semiconductor chip protection method

Abstract

[Problem] To provide a curable silicone-based gel composition to form a silicone-based gel having excellent thermal stability at high temperatures and having damping characteristics to protect a semiconductor chip from mechanical shock and vibration. [Solution] A curable silicone-based gel composition comprising: (A) an organopolysiloxane resin having a mass loss of 2.0 mass% or less when component (A) is exposed at 200 DEG C for 1 hour, the (A) organopolysiloxane resin not having a hydrosilylation reactive group; (B) a linear organopolysiloxane having an alkenyl group terminal; (C) a linear organohydrogenpolysiloxane (SiH-terminal); (D) a Q-branched organopolysiloxane having at least three silicon-bonded alkenyl groups on its molecular terminus; and (E) a hydrosilylation reaction catalyst.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and all advantages of U.S. Provisional Patent Application No. 63 / 391,137, filed on July 21, 2022, the contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to a curable silicone-based gel composition and a silicone-based gel used as an encapsulant for electronic products for sealing or filling electrical or electronic parts, and more specifically to a curable silicone-based gel composition that can form a silicone-based gel, which has excellent thermal stability compared to conventionally known silicone gels, can inhibit the occurrence of cracks in the silicone gel caused by high temperatures exceeding 200°C for hundreds of hours or thermal shock, and has excellent damping properties to protect semiconductor chips from mechanical shock and vibration, which is derived from the reduced cross-linking density in the cured silicone-based gel. Background Art

[0004] Silicone gels are known in the art and can protect electronic components from moisture, dust, shock, vibration and other harsh environmental factors, thereby extending service life and reliability. As a result, silicone gels are often used to seal and protect electronic system components, especially those with delicate components. Silicone gels are delivered commercially as 1-part or 2-part liquid formulations, which are then dispensed and cured in place to form a reticulated elastomeric silicone gel. Hydrosilylation chemistry is generally the existing reaction of choice for silicone gels, so curing can be achieved at room temperature or with thermal acceleration. Silicone gels combine the stress relief qualities of a fluid with the dimensional stability of an elastomer and minimal shrinkage in a solvent-free and byproduct-free solution.

[0005] Silicone gel compositions have been widely used to prepare silicone gels for use as sealants and fillers for electrical or electronic parts. In view of the myriad conditions and industries in which such electrical or electronic parts are used, it is increasingly desirable for silicone gels to have excellent thermal stability, including at temperatures of 200°C. However, conventional silicone gels are susceptible to cracking when exposed to such elevated temperatures for extended periods of time, which is undesirable.

[0006] One effort to improve the thermal stability of conventional silicone gels has been to incorporate non-functionalized polydimethylsiloxanes, which reduce the crosslink density. However, while the use of non-functionalized polydimethylsiloxanes can reduce the crosslink density of conventional silicone gels, their use also undesirably affects other performance properties of conventional silicone gels, such as modulus. Another effort has been to incorporate functionalized resins into silicone gel compositions, which become part of the crosslinked matrix of the silicone gel formed upon curing. While the use of functionalized resins provides the desired modulus, their use does not provide adequate thermal stability and crack resistance at elevated temperatures. Summary of the invention

[0007] The present invention discloses a curable silicone-based gel composition, which comprises (A) an organopolysiloxane resin, wherein the mass loss of the organopolysiloxane resin when the component (A) is exposed to 200° C. for 1 hour is 2.0% by mass or less and is represented by the following formula:

[0008] (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e

[0009] Each R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturation in the group; each R 2 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a, b, c, d and e are numbers satisfying the following conditions: 0.10≤a≤0.60, 0.0≤b≤0.70, 0.0≤c≤0.80, 0.10≤d≤0.65, 0≤e≤0.05, and a+b+c+d=1. The composition further comprises (B) a linear organopolysiloxane having only two silicon-bonded alkenyl groups at its molecular terminals and represented by the following formula:

[0010] (R 3 R 1 2SiO 1 / 2 )(R 1 2SiO 2 / 2 ) n (R 3 R 12SiO 1 / 2 )

[0011] Each R 1 are independently selected and defined above; each R 3 is independently an alkenyl group having 2 to 10 carbon atoms; and the subscript n is a number from 10 to 1000. The composition further comprises (C) a linear organohydrogenpolysiloxane having only two silicon-bonded hydrogen atoms at its molecular end and having a viscosity at 25° C. of 2 to 10,000 mPa·s. In addition, the composition comprises (D) a Q-branched organopolysiloxane having at least three silicon-bonded alkenyl groups at its molecular end and represented by the following formula:

[0012] (SiO 4 / 2 )[(R 1 2SiO 2 / 2 ) m (R 4 3SiO 1 / 2 )]4

[0013] Each R 1 are independently selected and defined above; each R 4 Independently for R 1 or an alkenyl group having 2 to 10 carbon atoms, provided that R 4 At least three of are alkenyl groups; and each m is independently a number from 5 to 200. Finally, the composition comprises (E) a hydrosilylation reaction catalyst in an amount sufficient for the curing reaction in components (A) to (D).

[0014] Also disclosed are an encapsulant for electronic products comprising the curable silicone-based gel composition, and a silicone-based gel prepared by curing the curable silicone-based gel composition.

[0015] Also provided is an electronic product comprising the encapsulant or the silicone-based gel.

[0016] Finally, a protection method for semiconductor chips is provided, characterized in that the semiconductor chips are protected by using the curable silicone-based gel composition, the encapsulant or the silicone-based gel.

[0017] Issues to be resolved

[0018] As electronic components become more complex and power density requirements rise, the need for better damping properties and thermal stability requirements for silicone gel materials is increasing.

[0019] Most conventional silicone gel materials ensure reliable performance up to 150° C., but the industry is increasingly seeking silicone gel materials that are stable at temperatures up to 200° C. Conventional silicone gel materials show signs of failure under such conditions, including the formation of cracks or voids, which can impair performance.

[0020] The damping properties of silicone gels provide a degree of protection against mechanical shock and vibration. Damping properties can be improved by reducing the crosslink density of silicone gels. Incorporation of non-functionalized ingredients, such as trimethylsiloxy-terminated polydimethylsiloxane, is one of the technical approaches to reduce the crosslink density; however, this technical approach is usually accompanied by a compromise of other properties, such as storage modulus (G'), which represents the stiffness of the material. Therefore, efforts to improve damping properties have resulted in undesirable effects on storage modulus and other performance properties.

[0021] Methods used to solve problems

[0022] As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a composition comprising: (A) an organopolysiloxane resin having no hydrosilylation-reactive group and having a mass loss of 2.0% by mass or less when exposed at 200° C. for 1 hour, in combination with (B) a linear organopolysiloxane having only two silicon-bonded alkenyl groups at its molecular terminals; (C) a linear organohydrogenpolysiloxane having only two silicon-bonded hydrogen atoms at its molecular terminals and having a viscosity at 25° C. of 2 MPa·s to 10,000 MPa·s; (D) a Q-branched organopolysiloxane having at least three silicon-bonded alkenyl groups at its molecular terminals; and (E) a hydrosilylation reaction catalyst.

[0023] Effects of the Invention

[0024] The curable silicone-based gel composition of the present invention can be cured into a silicone-based gel having excellent thermal stability and damping properties at high temperatures to protect semiconductor chips from mechanical shock or vibration. Therefore, this curable silicone-based gel composition can be used as an encapsulant applied to or used for electronic products, and an electronic product having the encapsulant or the silicone-based gel is provided. Moreover, the present invention can provide a method for protecting a semiconductor wafer, characterized in that a curable silicone-based gel composition, an encapsulant applied to an electronic product, or a silicone-based gel is used. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Various advantages and aspects of the present disclosure may be understood from the following detailed description when considered in conjunction with the accompanying drawings, in which:

[0026] Figure 1 The cured silicone gels of Examples 1-3 (shown as "INV1" to "INV3") are shown to be crack-free both initially and after 744 hours of heat aging;

[0027] Figure 2 The cured silicone gels of Examples 4-7 (shown as "INV4" to "INV7") are shown to be crack-free both initially and after 744 hours of heat aging; and

[0028] Figure 3 The cured silicone gels of Comparative Examples 1-3 (shown as "Comp 1" to "Comp 3") are shown initially and after 744 hours of heat aging (in a cracked state after aging). DETAILED DESCRIPTION

[0029] The present disclosure provides a curable silicone-based gel composition. The composition can be cured to obtain a silicone-based gel having excellent physical properties (including thermal stability and damping properties). Therefore, the composition is particularly suitable for use in or as an encapsulant for electronic components and articles. However, the end use of the composition and the silicone-based gel formed therefrom is not limited thereto. In addition, the composition of the present disclosure is also characterized in that it has hot melt properties as a whole. In the present disclosure, unless otherwise specified, "having hot melt properties" means having a softening point of 50°C to 200°C, having a melt viscosity at 150°C (suitably, a melt viscosity of less than 1,000 Pa·s) and having flow properties.

[0030] The composition of the present invention comprises (A) an organopolysiloxane resin represented by the following formula:

[0031] (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e

[0032] Each R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturation in the group; each R 2are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a, b, c, d and e are numbers satisfying the following conditions: 0.10≤a≤0.60, 0.0≤b≤0.70, 0.0≤c≤0.80, 0.10≤d≤0.65, 0≤e≤0.05, and a+b+c+d=1).

[0033] As will be appreciated by those skilled in the art, organopolysiloxane resins contain inorganic silicon-oxygen-silicon groups (i.e., -Si-O-Si-) with organosilicon and / or organic side groups attached to silicon atoms in M, D, and T siloxy units. Organopolysiloxane resins are typically characterized by the number, type, and / or ratio of [M], [D], [T], and / or [Q] units per siloxy group (each of which represents a structural unit for a respective functional group present in the organopolysiloxane resin). Specifically, [M] represents a general formula R″3SiO 1 / 2 [D] represents the general formula R″2SiO 2 / 2 [T] represents the general formula R″SiO 3 / 2 [Q] represents a trifunctional unit of the general formula SiO 4 / 2 The tetrafunctional unit is shown in the following general structure:

[0034]

[0035] In these general structural parts, each R" is independently a monovalent or polyvalent substituent. As understood in the art, there is no particular limitation on the specific substituents suitable for each R" (e.g., it can be monatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, etc., and various combinations thereof).

[0036] Those skilled in the art understand how [M], [D], [T], and [Q] units and their relative proportions (i.e., mole fractions) affect and control the structure of the siloxane, and that polysiloxanes can generally be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or resinous, depending on the selection of [M], [D], [T], and / or [Q] units therein. For example, [T] units and / or [Q] units are present in an organopolysiloxane resin, whereas a linear organopolysiloxane generally does not contain such [T] units and / or [Q] units.

[0037] In the (A) organopolysiloxane resin, each R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturation in the group. 1(A) The organopolysiloxane generally does not contain functional groups capable of hydrosilylation (i.e., silicon-bonded ethylenically unsaturated groups and silicon-bonded hydrogen atoms). Generally, R 1 The monovalent hydrocarbon group of may be independently linear, branched, cyclic or a combination thereof. Cyclic hydrocarbon groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbon groups may be independently monocyclic or polycyclic. An example of a combination of linear and cyclic hydrocarbon groups is an aralkyl group. General examples of monovalent hydrocarbon groups without aliphatic unsaturated groups include alkyl groups, aryl groups, halogenated carbon groups, etc., and their derivatives, modifications and combinations. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl and / or tert-pentyl), hexyl, heptyl, octyl, etc. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl and cycloheptyl. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl and dimethylphenyl. The example of suitable monovalent halogenated hydrocarbon group (that is, halogenated carbon group) includes halogenated alkyl group, aryl group and their combination.The example of halogenated alkyl group includes the above-mentioned alkyl group in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl.The specific example of halogenated alkyl group includes fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl and 2,3-dichlorocyclopentyl groups, and their derivatives. Examples of halogenated aryl groups include the above aryl groups in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups. In a specific embodiment, each R 1 Independently selected from alkyl groups having 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to 2, alternatively 1 carbon atom.

[0038] When (A) the organopolysiloxane resin is prepared by hydrolysis and condensation of silane, 2 O 1 / 2 ) is usually inherently present. For example, when preparing the (A) organopolysiloxane resin, the Q siloxy unit precursor may not be completely condensed, thus resulting in a Si-OR 2T silyloxy units with fewer than four siloxane bonds. The moiety represented by (R 2 O 1 / 2 ) may be absent from the (A) organopolysiloxane resin, depending on its method of preparation.

[0039] As described above, the subscripts a, b, c, d, and e are numbers that satisfy the following conditions: 0.10 ≤ a ≤ 0.60, 0.0 ≤ b ≤ 0.70, 0.0 ≤ c ≤ 0.80, 0.10 ≤ d ≤ 0.65, 0 ≤ e ≤ 0.05, and a + b + c + d = 1. In specific embodiments, 0.10 ≤ a ≤ 0.60, alternatively 0.15 ≤ a ≤ 0.60, alternatively 0.20 ≤ a ≤ 0.60, alternatively 0.25 ≤ a ≤ 0.60, alternatively 0.30 ≤ a ≤ 0.60, alternatively 0.35 ≤ a ≤ 0.60, alternatively 0.40 ≤ a ≤ 0.60, alternatively 0.40 ≤ a ≤ 0.55. In these or other embodiments, 0.0 ≤ b ≤ 0.70, alternatively 0.0 ≤ b ≤ 0.60, alternatively 0.0 ≤ b ≤ 0.50, alternatively 0.0 ≤ b ≤ 0.40, alternatively 0.0 ≤ b ≤ 0.30, alternatively 0.0 ≤ b ≤ 0.20, alternatively 0.0 ≤ b ≤ 0.10, alternatively 0.0 ≤ b ≤ 0.05, alternatively 0.0 < b ≤ 0.05, alternatively b is 0. In these or other embodiments, 0.0 ≤ c ≤ 0.80, alternatively 0.0 ≤ c ≤ 0.70, alternatively 0.0 ≤ c ≤ 0.60, alternatively 0.0 ≤ c ≤ 0.50, alternatively 0.0 ≤ c ≤ 0.40, alternatively 0.0 ≤ c ≤ 0.30, alternatively 0.0 ≤ c ≤ 0.20, alternatively 0.0 ≤ c ≤ 0.10, alternatively 0.0 ≤ c ≤ 0.05, alternatively 0.0 < c ≤ 0.05, alternatively c is 0. In these or other embodiments, 0.10 ≤ d ≤ 0.65, alternatively 0.15 ≤ d ≤ 0.65, alternatively 0.20 ≤ d ≤ 0.65, alternatively 0.25 ≤ d ≤ 0.65, alternatively 0.30 ≤ d ≤ 0.65, alternatively 0.35 ≤ d ≤ 0.65, alternatively 0.40 ≤ d ≤ 0.60, alternatively 0.45 ≤ d ≤ 0.55. In these or other embodiments, 0.0 ≤ e ≤ 0.05, alternatively 0.0 < e ≤ 0.05, alternatively e is 0.

[0040] As will be understood in view of the description herein, in specific embodiments, the (A) organopolysiloxane resin may be classified or otherwise referred to as an MQ resin, where as introduced above, M represents a monofunctionalized silyloxy unit and Q represents a tetrafunctionalized silyloxy unit (i.e., SiO 4 / 2Such MQ resins are known in the art as macromolecular polymers consisting primarily of M and Q units and optionally a limited number of D and / or T units (e.g., ≤20 mol %, alternatively ≤15 mol %, alternatively ≤10 mol %, alternatively ≤5 mol %), and are typically present in solid (e.g., powder or flake) form unless placed in a solvent. These MQ resins are generally of the general formula [M] x [Q] simply means that the subscript x refers to the molar ratio of M siloxy units relative to Q siloxy units when the molar number of Q siloxy units is normalized to 1. In such cases, the greater the value of x, the smaller the crosslinking density of the MQ resin. Vice versa, because when the value of x decreases, the number of M siloxy units decreases, and therefore more Q siloxy units are networked without being terminated by M siloxy units. However, it should be recognized that the normalized content of Q siloxy units does not imply or limit the MQ resin to only one Q unit. On the contrary, MQ resins generally include a plurality of Q siloxy units that are aggregated or bonded together. In certain embodiments, when (A) the organopolysiloxane resin is a MQ resin, x is 0.5 to 1.5, alternatively 0.6 to 1.4, alternatively 0.7 to 1.3, alternatively 0.8 to 1.2, alternatively 0.9 to 1.1.

[0041] In certain embodiments, the weight average molecular weight (M) of (A) the organopolysiloxane is w ) is greater than 1,000 g / mol to 100,000 g / mol, alternatively greater than 5,000 g / mol to 50,000 g / mol, alternatively 10,000 g / mol to 30,000 g / mol, alternatively 14,000 g / mol to 20,000 g / mol. The weight average molecular weight can be readily determined based on polystyrene standards using gel permeation chromatography (GPC) techniques.

[0042] The mass loss of component (A) when exposed to 200°C for 1 hour is 2.0% by mass or less. The mass loss rate of component (A) when exposed to 200°C for 1 hour is 2.0% by mass or less, which means that the amount of volatile components of component (A) is low. The organopolysiloxane resin (A) has a high content of specific branched siloxane units (SiO 4 / 2) or Q siloxy units, wherein the amount of volatile components in component (A) is very low. Specifically, the mass loss rate of component (A) when exposed to 200°C for 1 hour is 2.0 mass % or less, alternatively 1.5 mass % or less, alternatively 1.0 mass % or less. The mass loss is simply measured based on the mass of component (A) before exposing component (A) to a temperature of 200°C for 1 hour compared to the mass after exposing component (A) to a temperature of 200°C for 1 hour. In other words, the mass loss is the total mass of component (A) (if any) lost after exposing component (A) to a temperature of 200°C for 1 hour. Generally, exposing conventional organopolysiloxane resins to elevated temperatures results in a decrease in mass. There is no particular requirement for exposing component (A) to a temperature of 200°C for 1 hour to determine the mass loss. Any heat source, such as an oven, may be utilized. In addition, environmental conditions may be utilized, such as component (A) may be exposed to air, atmospheric pressure, relative humidity, etc. while heating component (A). In a specific embodiment, when measuring the mass loss of component (A), the environmental conditions are not controlled except for the temperature. The mass loss of component (A) is measured based on the organopolysiloxane resin of component (A) in pure form, i.e., any vehicle or solvent present in component (A) is removed before measuring or determining the mass loss, because the volatilization of any vehicle or solvent is not considered to affect the mass loss of component (A). In a specific embodiment, the mass loss of component (A) is based only on the silicon-based compound volatilized from component (A) after exposure to a temperature of 200° C. for 1 hour. The silicon-based compound is any compound containing silicon atoms.

[0043] For example, typically, in the production process of conventional organopolysiloxane resins containing a large number of branched siloxane units, volatile low molecular weight components are produced as by-products from the condensation of silane compounds, which are physically mixed into and with conventional organopolysiloxane resins. For example, conventional organopolysiloxane resins are typically used as physical matrices containing by-products. These by-products, especially small molecules with few siloxy units, are considered to be volatile components. However, these volatile components have the effect of greatly reducing the hardness of the cured product obtained by curing a composition containing such conventional organopolysiloxane resins, because the volatile components do not contribute to the curing or crosslinking density. Therefore, when the cured product is exposed to a temperature exceeding 150°C for a long time, the by-products contained in or with the conventional organopolysiloxane resin will volatilize, and therefore, the hardness of the cured product is significantly reduced. In addition, when the network of the cured product contains a large amount of silanes such as SiO 4 / 2 When the siloxane units are expressed, the cured product tends to be extremely brittle in hardness and thus also embrittlement occurs.

[0044] By using (A) an organopolysiloxane resin in the composition, a cured product that does not tend to increase in hardness and embrittlement even when exposed to a temperature exceeding 150°C for a long time can be provided. Therefore, when the mass loss of component (A) exceeds the upper limit when exposed at 200°C for 1 hour, the hardness of the resulting cured product increases significantly, especially at high temperatures, and tends to embrittle. It should be noted that the lower limit of the mass loss rate of component (A) is usually 0.0% by mass or does not contain volatile low molecular weight components, but in actual use, the hardness change of the cured product can be fully suppressed in the range of 0.1% to 2.0% by mass, in the range of 0.2% to 1.5% by mass, and in the range of 0.3% to 0.8% by mass. When the mass loss rate of component (A) is 0.0% by mass, component (A) may be substantially composed of an organopolysiloxane resin, alternatively composed of an organopolysiloxane resin.

[0045] The type of volatile low molecular weight component is not particularly limited, but since the organopolysiloxane resin of the present invention contains a large amount of SiO 4 / 2 The branched siloxane unit (Q unit) represented by M4Q can be easily separated from the volatile siloxane component represented by R3SiO 1 / 2 The mass reduction ratio is typically achieved by removing a volatile low molecular weight component or a volatile siloxane component from the (A) organopolysiloxane resin to obtain component (A).

[0046] Component (A) may comprise a combination of two or more different organopolysiloxane resins that differ in at least one characteristic such as structure, molecular weight, monovalent groups bonded to silicon atoms, and the like.

[0047] In certain embodiments, component (A) may also include a vehicle to carry, dissolve or partially dissolve the organopolysiloxane resin. If used, the vehicle is typically an organic fluid, which typically includes an organic oil containing volatile and / or semi-volatile hydrocarbons, esters and / or ethers. General examples of such organic fluids include volatile hydrocarbon oils, such as C6-C 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8-C 16 Branched chain esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), and their derivatives, modifications, and combinations. Other examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols with more than 3 carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, aromatic halides, and combinations thereof. Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 -C13 )、Isopar H(C 11 -C 12 ), 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, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octadecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, octyl palmitate, and combinations thereof.

[0048] In some embodiments, the medium comprises an organic solvent, alternatively an organic solvent. Examples of organic solvents include those comprising alcohols such as methanol, ethanol, isopropanol, butanol or n-propanol; ketones such as acetone, methyl ethyl ketone and 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; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane and dichloromethane; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; white spirit; solvent oil; naphtha; N-methylpyrrolidone; etc., and derivatives, modifications and combinations thereof.

[0049] The amount of vehicle present in component (A) depends on various factors (e.g., the choice of organopolysiloxane resin, the curing conditions to which the composition is intended to be exposed, etc.), and can be easily determined by a person skilled in the art. Typically, when present, component (A) comprises a vehicle in an amount of 1% to 50% by weight, alternatively 20% to 50% by weight, alternatively 30% to 40% by weight, based on the total weight of component (A). However, typically, component (A) does not contain a vehicle, and the organopolysiloxane resin is used in the composition in pure or dry form. Alternatively, component (A) may initially contain a vehicle, and the vehicle may be removed from component (A) and / or the composition during the preparation of the composition prior to the final use of the composition.

[0050] The composition typically comprises component (A) in an amount of 1 to 40 wt%, alternatively 2 to 40 wt%, alternatively 3 to 40 wt%, alternatively 4 to 40 wt%, alternatively 5 to 40 wt%, alternatively 6 to 40 wt%, alternatively 3 to 30 wt%, alternatively 4 to 30 wt%, alternatively 5 to 30 wt%, alternatively 6 to 30 wt%, based on the total weight of the composition. These weight ranges are typically based only on the organopolysiloxane resin of component (A), and not on any vehicle that may be present in component (A).

[0051] The composition also comprises (B) a linear organopolysiloxane having only two silicon-bonded alkenyl groups at the ends of its molecule. In other words, component (B) does not include silicon-bonded alkenyl groups at the side positions, i.e., alkenyl groups bonded to the silicon atoms in the D siloxy units. The linear organopolysiloxane is represented by the formula:

[0052] (R 3 R 1 2SiO 1 / 2 )(R 1 2SiO 2 / 2 ) n (R 3 R 1 2SiO 1 / 2 ),

[0053] Each R 1 are independently selected and defined above; each R 3 is independently an alkenyl group having 2 to 10 carbon atoms; and n is a number from 10 to 1000. As shown in the above formula, each terminal M unit of the linear organopolysiloxane of component (B) includes one alkenyl group, i.e., the linear organopolysiloxane has a total of two silicon-bonded alkenyl groups, rather than at each molecular terminal.

[0054] Relative to R 3 "Alkenyl" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples thereof include vinyl groups, allyl groups, hexenyl groups and octenyl groups. Various examples of olefinically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=CHCH2CH2- and H2C=CHCH2CH2CH2-. Typically, a double bond or olefinically unsaturated group is located at each R 3 The end of .

[0055] In a specific embodiment, each R of component (B) 1 Independently selected from alkyl groups having 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to 2, alternatively 1 carbon atom.

[0056] The subscript n defines the number of D siloxy units present in the linear organopolysiloxane of component (B), and may alternatively be referred to as the degree of polymerization of the linear organopolysiloxane. In certain embodiments, the subscript n is from 10 to 1000, alternatively from 50 to 750, alternatively from 100 to 500, alternatively from 150 to 450, alternatively from 200 to 400, alternatively from 250 to 350.

[0057] The linear organopolysiloxane of component (B) can be exemplified by dimethylpolysiloxane terminated at both molecular ends with dimethylvinylsiloxy groups, methylphenylpolysiloxane terminated at both molecular ends with dimethylvinylsiloxy groups, and / or a copolymer of methylphenylsiloxane terminated at both molecular ends with dimethylvinylsiloxy groups and dimethylsiloxane.

[0058] Alternatively, as a specific example of the linear organopolysiloxane of component (B), the linear organopolysiloxane may include an average formula of Vi(CH3)2SiO[(CH3)2SiO] n An organopolysiloxane of Si(CH3)2Vi or consisting thereof, wherein Vi indicates a vinyl group and the subscript n is defined above. With respect to the average formula, any methyl group may be replaced by a different monovalent hydrocarbon group, and any vinyl group may be replaced by any alkenyl group.

[0059] In a specific embodiment, component (B) has a viscosity at 25° C. of 10 MPa.s to 100,000 MPa.s, alternatively 10 MPa.s to 10,000 MPa.s, alternatively 50 MPa.s to 10,000 MPa.s. The viscosity can be measured at 25° C. by a Brookfield LV DV-E viscometer with a spindle selected to be suitable for the viscosity of substantially linear polyorganosiloxanes, i.e., RV-1 to RV-7.

[0060] Component (B) may comprise a combination of two or more different linear organopolysiloxanes that differ in at least one property such as structure, molecular weight, degree of polymerization, viscosity, and the like.

[0061] The composition typically comprises component (B) in an amount of 1 wt % to 60 wt %, alternatively 2 wt % to 55 wt %, alternatively 5 wt % to 50 wt %, alternatively 5 wt % to 40 wt %, alternatively 7.5 wt % to 35 wt %, based on the total weight of the composition.

[0062] The composition also includes (C) a linear organohydrogenpolysiloxane having only two silicon-bonded hydrogen atoms at its molecular ends. In other words, component (C) does not include silicon-bonded hydrogen atoms in the side positions, i.e., hydrogen atoms bonded to silicon atoms in the D siloxy units. The linear organohydrogenpolysiloxane having only hydrogen atoms bonded to silicon atoms at its molecular ends of component (C) serves as a crosslinker for the composition.

[0063] In a specific embodiment, the linear organohydrogenpolysiloxane has an average unit formula: (HR 1 2SiO 1 / 2 )(R 1 2SiO 2 / 2 ) n’ (HR 1 2SiO 1 / 2 ), where each R 1 is independently selected and defined above, and subscript n' is selected so that the linear organohydrogenpolysiloxane has a viscosity of 2 MPa.s to 10,000 MPa.s, alternatively 10 MPa.s to 10,000 MPa.s at 25°C. In specific embodiments, subscript n' is 1 to 500, alternatively 1 to 200, alternatively 1 to 150, alternatively 1 to 100, alternatively 1 to 50, alternatively 5 to 40, alternatively 10 to 30.

[0064] In another specific embodiment, the linear organohydrogenpolysiloxane has the following average formula:

[0065] H(CH3)2SiO[(CH3)2SiO] n’ Si(CH3)2H

[0066] wherein n' is as defined above. Component (C) may comprise a combination of two or more different linear organohydrogenpolysiloxanes that differ in at least one property such as structure, molecular weight, degree of polymerization, viscosity, and the like.

[0067] The composition typically comprises component (C) in an amount of 1 to 40 wt%, alternatively 2 to 30 wt%, alternatively 5 to 25 wt%, based on the total weight of the composition. Component (C) is typically present in an amount such that the molar ratio of silicon-bonded hydrogen atoms in component (C) to silicon-bonded alkenyl groups in component (B) and component (D) (described below) is 0.2:1 to 5:1, alternatively 0.8:1 to 1.2:1 (the number of moles of silicon-bonded hydrogen atoms in component (C) to the total number of moles of silicon-bonded alkenyl groups present in the other components of the composition).

[0068] In addition, the composition comprises (D) a Q-branched organopolysiloxane having at least three silicon-bonded alkenyl groups at the molecular ends thereof. With respect to component (D), the term "Q-branched" means that the branches in component (D) are composed of Q siloxy units, i.e., SiO 4 / 2 The Q-branched organopolysiloxane of component (D) is represented by the following formula:

[0069] (SiO 4 / 2 )[(R 1 2SiO 2 / 2 ) m (R 4 3SiO 1 / 2 )]4

[0070] Each R 1 are independently selected and defined above; each R 4 Independently for R 1 or an alkenyl group having 2 to 10 carbon atoms, provided that R 4 At least three of are alkenyl groups; and each subscript m is independently a number from 5 to 200. 1 Suitable examples of R 4 Illustrative examples of alkenyl groups.

[0071] Q-branched organopolysiloxanes generally comprise M siloxy units (i.e., (R 4 3SiO 1 / 2 ) siloxy units), D siloxy units (ie, (R 1 2SiO 2 / 2 ) siloxy units) and Q siloxy units (i.e., (SiO 4 / 2 ) siloxy units). Although the Q-branched organopolysiloxane includes one Q siloxy unit, due to the degree of polymerization (DP) in the Q-branched organopolysiloxane and the low mole fraction of the Q siloxy units present therein, the Q-branched organopolysiloxane is considered by those skilled in the art to be a branched silicone polymer rather than a silicone resin.

[0072] The degree of polymerization (DP) of the Q-branched organopolysiloxane is 20 to 800, alternatively 50 to 600, alternatively 100 to 400, alternatively 150 to 350, alternatively 175 to 325. As understood in the art, the DP of the Q-branched organopolysiloxane is the sum or aggregation of each m, which represents the number of D siloxy units in each linear branch of the Q-branched organopolysiloxane. The Q-branched organopolysiloxane includes a Q unit having four linear chains, which consists of D siloxy units terminated with M siloxy units. Each linear chain has an independently selected subscript m, and therefore the length or number of siloxy units in each linear chain is also independently selected. In certain embodiments, each subscript m is different. In other embodiments, each subscript m is the same.

[0073] The Q-branched organopolysiloxane of component (D) can also be represented by the following formula:

[0074] Si-[[OSiR 1 2] m [OSiR 4 3]]4

[0075] Each R 1 and R 4 is independently selected and defined above, and each subscript m is independently selected and defined above.

[0076] In a specific embodiment, each R 1 is a methyl group (Me), and each R 4 is a vinyl group (Vi). In these embodiments, the Q-branched organopolysiloxane of component (D) has the following general formula:

[0077] Si-[[OSiMe2] m [OSiMe2Vi]]4

[0078] wherein m is independently selected and defined above. However, as mentioned above, the M siloxy units and / or the D siloxy units may be different from each other.

[0079] Regardless of the choice of the Q-branched organopolysiloxane of component (D), the Q-branched organopolysiloxane has at least three 4 In certain embodiments, the Q-branched organopolysiloxane has from greater than 0 wt % to 7 wt %, alternatively from 0.1 wt % to 6 wt %, of R 4 This is usually when each R 4 For vinyl and each R 1 However, as is understood in the art, when R1 is a substance other than methyl (e.g. ethyl, aryl) and / or when R 2 When it is a species other than vinyl (e.g., allyl, hexenyl), the same number of alkenyl groups may constitute a smaller total weight %, which affects the molecular weight of the Q-branched organopolysiloxane. 4 The content of can be determined using silicon 29 nuclear magnetic resonance spectroscopy ( 29 SiNMR) to interpret and calculate.

[0080] Combinations of different Q-branched organopolysiloxanes may be used together as component (D).

[0081] In certain embodiments, the Q-branched organopolysiloxane has a viscosity at 25°C of greater than 0 MPa.s to less than 12,000 MPa.s, alternatively greater than 50 MPa.s to 10,000 MPa.s, alternatively greater than 50 MPa.s to 7,500 MPa.s, alternatively greater than 50 MPa.s to 5,000 MPa.s, alternatively greater than 50 MPa.s to 2,500 MPa.s, alternatively greater than 50 MPa.s to less than 1,000 MPa.s.

[0082] The composition generally comprises component (D) in an amount of 20 to 90 wt%, alternatively 30 to 80 wt%, alternatively 40 to 75 wt%, based on the total weight of the composition.

[0083] The composition further comprises (E) a hydrosilylation reaction catalyst. The (E) hydrosilylation reaction catalyst is not limited and may be any known hydrosilylation reaction catalyst for catalyzing a hydrosilylation reaction. A combination of different hydrosilylation reaction catalysts may be used.

[0084] The (E) hydrosilylation reaction catalyst may be located in or on a solid support. Examples of supports include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate), etc. The (E) hydrosilylation reaction catalyst may also be disposed in a medium, such as a solvent that dissolves the (E) hydrosilylation reaction catalyst, or alternatively a medium that only carries but does not dissolve the (E) hydrosilylation reaction catalyst. Such mediums are known in the art.

[0085] In specific embodiments, the (E) hydrosilylation reaction catalyst comprises platinum. In these embodiments, the (E) hydrosilylation reaction catalyst is exemplified by, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid and monohydric alcohols, bis(ethyl acetoacetate) platinum, bis(acetylacetonate) platinum, platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, and platinum compounds microencapsulated in a matrix or core-shell compound. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art, as exemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654, which are incorporated herein by reference in their entirety.

[0086] Complexes of platinum and organopolysiloxane suitable for use as (E) hydrosilylation catalysts include complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum. These complexes may be microencapsulated in a resin matrix. Alternatively, the (E) hydrosilylation catalyst may include a complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum. The (E) hydrosilylation catalyst may be prepared by a method comprising reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane or an olefin-platinum-silyl complex.

[0087] (E) The hydrosilylation catalyst may also or alternatively be a photoactivatable hydrosilylation catalyst that can initiate curing via irradiation and / or heating. The photoactivatable hydrosilylation catalyst may be any hydrosilylation catalyst that is particularly capable of catalyzing a hydrosilylation reaction when exposed to radiation having a wavelength of 150 nanometers to 800 nanometers (nm).

[0088] Specific examples of photoactivatable hydrosilylation reaction catalysts suitable for (E) hydrosilylation reaction catalysts include, but are not limited to, β-diketone platinum(II) complexes, such as bis(2,4-pentanedioate)platinum(II), bis(2,4-hexanedioate)platinum(II), bis(2,4-heptanedioate)platinum(II), bis(1-phenyl-1,3-succinate)platinum(II), bis(1,3-diphenyl-1,3-propanedioate)platinum(II), bis(1,1,5,5-tetramethylol)platinum(II), and bis(1,5-diphenyl-1,3-propanedioate). ,5-hexafluoro-2,4-pentanedioic acid) platinum (II); (η-cyclopentadienyl) trialkyl platinum complexes, such as (Cp) trimethyl platinum, (Cp) ethyldimethyl platinum, (Cp) triethyl platinum, (chloro-Cp) trimethyl platinum and (trimethylsilyl-Cp) trimethyl platinum, wherein Cp represents a cyclopentadienyl group; triazene oxide-transition metal complexes, such as Pt[C6H5NNNOCH3]4, Pt[p-CN-C6H4NNNOC6H 11 ]4. Pt[p-H3COC6H4NNNOC6H 11]4. Pt[p-CH3(CH2) x -C6H4NNNOCH3]4,1,5-cyclooctadiene.Pt[p-CN-C6H4NNNOC6H 11 ]2、1,5-cyclooctadiene.Pt[p-CH3O-C6H4NNNOCH3]2、[(C6H5)3P]3Rh[p-CN-C6H4NNNOC6H 11 ] and Pd[p-CH3(CH2) x —C6H4NNNOCH3]2, wherein x is 1, 3, 5, 11 or 17; (η-diolefin)(σ-aryl)platinum complexes such as (η 4 -1,5-cyclooctadienyl)diphenylplatinum, (η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η 4 -2,5-norbornene)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum and (η 4 Typically, the photoactivatable hydrosilylation catalyst is a Pt(II) β-diketone complex, and more typically, the catalyst is platinum(II) bis(2,4-pentanedioic acid).

[0089] (E) The hydrosilylation catalyst is present in the composition in a catalytic amount, i.e., an amount or quantity sufficient to promote its curing under the desired conditions. The hydrosilylation catalyst can be a single hydrosilylation catalyst or a mixture comprising two or more different hydrosilylation catalysts.

[0090] The catalytic amount of the (E) hydrosilylation reaction catalyst may be >0.01 ppm to 10,000 ppm; alternatively >1,000 ppm to 5,000 ppm. Alternatively, a typical catalytic amount of the (E) hydrosilylation reaction catalyst is 0.1 ppm to 5,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively >1 ppm to 1,000 ppm. Alternatively, the catalytic amount of the (E) hydrosilylation reaction catalyst may be 0.01 ppm to 1,000 ppm, alternatively 0.01 ppm to 100 ppm, alternatively 20 ppm to 200 ppm, and alternatively 0.01 ppm to 50 ppm of a platinum group metal; the above catalytic amounts are based on the total weight of the composition.

[0091] In certain embodiments, the composition further comprises (F) an adhesion promoter. Suitable adhesion promoters may include hydrocarbyl silanes such as alkoxy silanes, combinations of alkoxy silanes and hydroxyl functional polyorganosiloxanes, amino functional silanes, epoxy functional silanes, mercapto functional silanes, or combinations thereof. Adhesion promoters are known in the art and may include a silane having the formula R 5 a R 6 b Si(OR 7 ) 4-(a+b) Silane, where each R 5 are independently a monovalent organic group having at least 3 carbon atoms; R 6 contains at least one SiC-bonded substituent having an adhesion promoting group such as an amino, epoxy, mercapto or acrylate group; each R 7 is independently a monovalent organic group (e.g., methyl, ethyl, propyl, butyl, etc.); the value of subscript a ranges from 0 to 2; subscript b is 1 or 2; and the sum of (a+b) is not greater than 3. In certain embodiments, the (F) adhesion promoter comprises a partial condensate of the above silane. In these or other embodiments, the (F) adhesion promoter comprises a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0092] In some embodiments, the (F) adhesion promoter includes an unsaturated or epoxy-functional compound. In such embodiments, the (F) adhesion promoter may be or include an unsaturated or epoxy-functional alkoxysilane, such as those having formula (XIII): R 8 c Si(OR 9 ) (4-c) , where subscript c is 1, 2, or 3, and alternatively subscript c is 1. Each R 8 are independently monovalent organic groups, provided that at least one R 8 is an unsaturated organic group or an epoxy-functional organic group. 8 The epoxy-functional organic groups for R are exemplified by 3-glycidyloxypropyl and (epoxycyclohexyl)ethyl. 8 The unsaturated organic group is exemplified by 3-methacryloxypropyl, 3-acryloxypropyl, and an unsaturated monovalent hydrocarbon group such as vinyl, allyl, hexenyl, and undecenyl. 9 R is independently a saturated hydrocarbon group having 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. 9 Exemplified by methyl, ethyl, propyl and butyl.

[0093] Specific examples of suitable epoxy-functionalized alkoxysilanes include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and combinations thereof.

[0094] In some embodiments, the (F) adhesion promoter includes an epoxy-functional siloxane, such as a reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane (e.g., one of the above-mentioned alkoxysilanes), or a physical blend of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane. The (F) adhesion promoter may include a combination of epoxy-functional alkoxysilanes and epoxy-functional siloxanes. For example, the (F) adhesion promoter is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and a reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

[0095] In certain embodiments, the (F) adhesion promoter includes an amino-functional silane, such as an amino-functional alkoxysilane exemplified by: H2N(CH2)2Si(OCH3)3, H2N(CH2)2Si(OCH2CH3)3, H2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3, CH3NH(CH2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)5Si(OCH3)3, CH3NH(CH2)5Si(OCH2CH3)3 , H2N(CH2)2NH(CH2)3Si(OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3, CH3NH(CH2)2NH( CH2)3Si(OCH2CH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH3(OCH3)2 , H2N(CH2)2SiCH3(OCH2CH3)2, H2N(CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)5SiCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, N-(3-(trimethoxysilyl)propyl)ethylenediamine, and the like, and combinations thereof. In these or other embodiments, the (F) adhesion promoter includes a mercapto-functional alkoxysilane, such as 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

[0096] Further examples of adhesion promoters include reaction products of epoxyalkylalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and amino-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane, optionally with alkylalkoxysilanes such as methyltrimethoxysilane.

[0097] Exemplary adhesion promoters include reaction mixtures of amino group-containing organoalkoxysilanes and epoxy group-containing organoalkoxysilanes. Such reaction mixtures are disclosed in Japanese Patent Application Publication S52-8854 B and Japanese Unexamined Patent Application Publication H10-195085A.

[0098] In terms of molar ratio, the ratio of the alkoxysilane having an organic group containing an amino group to the alkoxysilane having an organic group containing an epoxy group is typically in the range of (1:1.5) to (1:5), alternatively in the range of (1:2) to (1:4). This component can be easily synthesized by mixing the alkoxysilane having an organic group containing an amino group and the alkoxysilane having an organic group containing an epoxy group as mentioned above, and reacting them at room temperature or by heating.

[0099] In particular, when an alkoxysilane having an organic group containing an amino group is reacted with an alkoxysilane having an organic group containing an epoxy group by the method described in Japanese Unexamined Patent Application H10-195085A, the present invention may include a carbasilatrane derivative obtained by cyclization through an alcohol exchange reaction and represented by the following general formula:

[0100]

[0101] Where R 1 is an alkyl group, an alkenyl group or an alkoxy group, R 2 are the same or different groups selected from the groups represented by the following general formula:

[0102]

[0103] Where R 4 is an alkylene group or an alkyleneoxyalkylene group, R 5 is a monovalent hydrocarbon group, R 6 is an alkyl group, and a is 0, 1 or 2, or

[0104] -R 7 -OR 8

[0105] Where R 7 is an alkylene group, R 8 is an alkyl group, an alkenyl group or an acyl group, and R3 are the same or different hydrogen atoms or alkyl groups. Examples of the carbazosilatricyclic derivative may include carbazosilatricyclic derivatives having a silicon-bonded alkoxy group or a silicon-bonded alkenyl group per molecule represented by the following structure.

[0106]

[0107] wherein Rc is a group selected from a methoxy group, an ethoxy group, a vinyl group, an allyl group and a hexenyl group.

[0108] Furthermore, in the present invention, a silatricyclic derivative represented by the following structural formula may be used as an adhesion-imparting agent:

[0109]

[0110] The R in the formula 1 are the same or different hydrogen atoms or alkyl groups, and R 1 Usually a hydrogen atom or a methyl group. 2 are the same or different groups selected from the group consisting of hydrogen atoms, alkyl groups and organic groups containing alkoxysilyl groups represented by the following general formula:

[0111] -R 4 -Si(OR 5 ) x R 6 (3-x)

[0112] Where R 2 At least one of them is an organic group containing an alkoxysilyl group. 2 Examples of the alkyl group of include a methyl group and the like. 2 In the organic group containing an alkoxysilyl group, R 4 is a divalent organic group, and examples include an alkylene group or an alkyleneoxyalkylene group. Typical examples are an ethylene group, a propylene group, a butylene group, a methyleneoxypropylene group, and a methyleneoxypentylene group. 5 is an alkyl group having 1 to 10 carbon atoms, and is usually a methyl group or an ethyl group. 6 is a substituted or unsubstituted monovalent hydrocarbon group, and is typically a methyl group. In addition, x in the formula is 1, 2 or 3, and is typically 3.

[0113] R 2 Examples of such an alkoxysilyl group-containing organic group include the following groups.

[0114] -(CH2)2Si(OCH3)3-(CH2)2Si(OCH3)2CH3

[0115] -(CH2)3Si(OC2H5)3-(CH2)3Si(OC2H5)(CH3)2

[0116] -CH2O(CH2)3Si(OCH3)3

[0117] -CH2O(CH2)3Si(OC2H5)3

[0118] -CH2O(CH2)3Si(OCH3)2CH3

[0119] -CH2O(CH2)3Si(OC2H5)2CH3

[0120] -CH2OCH2Si(OCH3)3-CH2OCH2Si(OCH3)(CH3)2

[0121] When used, the (F) adhesion promoter is present in the composition in an amount of greater than 0 wt % to 3 wt %, alternatively 0.001 wt % to 2.0 wt %, based on the total weight of the composition.

[0122] In certain embodiments, the composition further comprises (G) (g1) an alkali metal silanolate and (g2) a 1 Cl y The chloride salt represented by (R 5 COO y M 1 represents the reaction product of at least one salt of a carboxylate, wherein each R 5 are the same or different monovalent hydrocarbon groups, M 1 is cerium or a rare earth metal mixture containing cerium as a main component, and y depends on M 1 The valence of cerium is in the range of 1 to 3. By "major component" is meant that the rare earth metal mixture contains cerium in an amount greater than the amount of any other rare earth metal present in the mixture.

[0123] If used, component (G) is used to enhance the heat resistance of the composition and the cured product formed therefrom. In a specific embodiment, component (G) contains 0.5% to 5.0% by mass of cerium (metal). The alkali metal silicon alkoxide (g1) is generally an alkali metal silicon alkoxide compound obtained by ring-opening at least one cyclic organopolysiloxane using an alkali metal hydroxide, and then further reacting the resulting product with an organopolysiloxane having a viscosity in the range of 10mPa·s to 1,000,000, alternatively 100mPa·s to 10,000mPa·s at 25°C. The cyclic organopolysiloxane is not particularly limited and generally includes 3 to 8 siloxy units. Examples of cyclic organopolysiloxanes include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7-tetra(3-methacryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-acryloyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(N,N-bis(lauryl)-3-aminopropyl)tetramethylcyclotetrasiloxane, etc. In addition, a mixture of different cyclic organopolysiloxanes may be used.

[0124] The alkali metal hydroxide is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, etc. The amount of the alkali metal hydroxide is usually 0.1 parts by mass to 10.0 parts by mass per 100 parts by mass of the cyclic organopolysiloxane.

[0125] Any conventionally known organopolysiloxane having a viscosity in the range of 100 mPa·s to 1,000,000 mPa·s at 25°C can be used as the organopolysiloxane to form the alkali metal siliconate (g1), and the organopolysiloxane is substantially a straight chain or branched chain organopolysiloxane which is liquid at room temperature and has a repeating diorganopolysiloxane unit (straight chain structure) as a main component. The organic group (i.e., substituted or unsubstituted monovalent hydrocarbon group) bonded to the silicon atom may be the same organic group exemplified above. Examples of organopolysiloxanes include organopolysiloxanes whose molecular ends are capped with triorganosiloxy groups (including trialkylsiloxy groups such as trimethylsiloxy groups, alkenyldialkylsiloxy groups such as vinyldimethylsiloxy groups, dienylalkylsiloxy groups such as divinylmethylsiloxy groups, trialenylsiloxy groups such as trivinylsiloxy groups, etc.), or organopolysiloxanes whose molecular ends are capped with hydroxyl groups, alkoxy groups, etc.

[0126] The salt of component (g2) is composed of M 1 Cl y Chloride salt represented by (R 5 COO y M 1 represents a carboxylate, wherein each R 5 are the same or different monovalent hydrocarbon groups, M 1 is cerium or a rare earth metal mixture containing cerium as a main component, and y depends on M 1 The valence of M is in the range of 1 to 3. 1 "Cerium" refers to a mixture of cerium or a plurality of rare earth elements containing cerium as a main component, and examples include cerium salts of 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, stearic acid, etc. Carboxylates can be used as organic solvent solutions. Examples of organic solvents include petroleum-based solvents such as standard solvent, solvent oil, light petroleum and petroleum ether, and aromatic solvents such as toluene and xylene.

[0127] The amount of the salt of component (g2) is not particularly limited, but is generally in an amount providing 0.05 to 5 parts by mass, alternatively 0.1 to 3 parts by mass, of M per 100 parts by mass of the total component (g1) described above. 1 Component (G) can be obtained by mixing components (g1) and (g2) and then heat-treating the mixture at 150°C or higher. The heating temperature of the heat treatment is generally 150°C to 310°C, alternatively 200°C to 305°C, alternatively 250°C to 300°C.

[0128] When used, component (G) is present in the composition in an amount of greater than 0 wt% to 3 wt%, alternatively 0.001 wt% to 2.0 wt%, based on the total weight of the composition.

[0129] The curable silicone composition of the present invention may also contain (H) fillers and / or (I) pigments. The (H) filler is not limited and may be, for example, a reinforcing filler, a compatibilizing filler, a thermally conductive filler, an electrically conductive filler, a flame retardant filler, an acid accepting filler, a rheology modifying filler, a phosphor, a coloring filler, a mineral filler, a glass filler, a carbon filler, or a combination thereof. The choice of the (H) filler is generally a function of the cured product to be formed with the composition and the end-use application of the cured product.

[0130] The (H) filler may be untreated, pretreated, or added in combination with an optional filler treating agent as described below, and when so added, the (H) filler may be treated in situ or prior to incorporating the (H) filler into the composition. The (H) filler may be a single filler or a combination of two or more fillers differing in at least one characteristic, such as filler type, method of preparation, treatment or surface chemistry, filler composition, filler shape, filler surface area, average particle size, or particle size distribution.

[0131] The shape and size of the (H) filler and / or (I) pigment are also not particularly limited. For example, the (H) filler can be spherical, rectangular, oval, irregular, and can be in the form of, for example, powder, flour, fiber, flakes, fragments, shavings, strands, scrims, wafers, wool, straw, particles, and combinations thereof. The size and shape are generally selected based on the type of (H) filler utilized, the selection of other components included in the composition, and the end-use application of the cured product formed therewith.

[0132] Non-limiting examples of fillers that can be used as reinforcing fillers include reinforcing silica fillers, such as fumed silica, silica aerogels, silica xerogels, and precipitated silica. Fumed silica is known in the art and is commercially available; for example, fumed silica sold under the trade name CAB-O-SIL by Cabot Corporation of Massachusetts, USA.

[0133] Non-limiting examples of fillers that can be used as expanding or reinforcing fillers include quartz and / or crushed quartz, alumina, magnesium oxide, silica (e.g., pyrogenic, ground, precipitated silica), hydrated magnesium silicate, magnesium carbonate, dolomite, silicone resins, wollastonite, saponite, kaolin, china clay, muscovite, phlogopite, halloysite (hydrated aluminum silicate), aluminum silicate, sodium aluminosilicate, glass (fibers, beads or particles, including recycled glass, e.g., from wind turbines or other sources), clay, magnetite, hematite, calcium carbonate (such as precipitated , pyrogenic and / or ground calcium carbonate), calcium sulfate, barium sulfate, calcium metasilicate, zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, chalk, titanium dioxide, zirconium oxide, sand, carbon black, graphite, anthracite, coal, lignite, charcoal, activated carbon, non-functionalized silicone resins, aluminum oxide, silver, metal powders, magnesium oxide, magnesium hydroxide, magnesium oxysulfate fibers, aluminum trihydrate, aluminum hydroxide, coated fillers, carbon fibers (including recycled carbon fibers, e.g. from the aircraft and / or automotive industries), aromatic polyamides (such as chopped KEVLAR TM or Twaron TM ), nylon fibers, mineral fillers or pigments (e.g., titanium dioxide, non-hydrated, partially hydrated or hydrated fluorides, chlorides, bromides, iodides, chromates, carbonates, hydroxides, phosphates, hydrogen phosphates, nitrates, oxides and sulfates of sodium, potassium, magnesium, calcium and barium; zinc oxide, antimony pentoxide, antimony trioxide, beryllium oxide, chromium oxide, lithopone, boric acid or borates (such as zinc borate, barium metaborate or aluminum borate), mixed metal oxides (such as vermiculite, bentonite, pumice, perlite, fly ash, clay and silica gel); rice husk ash, ceramics and zeolites, metals (such as aluminum flakes or powders, bronze powders, copper, gold, molybdenum, nickel, silver powders or flakes), stainless steel powders, tungsten, barium titanate, silica-carbon black composites, functionalized carbon nanotubes, cement, slate powder, pyrophyllite, sepiolite, zinc stannate, zinc sulfide) and combinations thereof. Alternatively, the expanding or reinforcing filler may be selected from the group consisting of calcium carbonate, talc, and combinations thereof.

[0134] As is known in the art, certain fillers can be used as pigments. By way of example, white pigments can include metal oxides such as titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, magnesium oxide, etc.; hollow fillers such as glass spheres, glass beads, etc.; and additionally, barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. Such components can be considered fillers and / or pigments.

[0135] Extending fillers are known in the art and are commercially available; for example, ground silica sold under the trade name MIN-U-SIL by US Silica of Berkeley Springs, WV. Suitable precipitated calcium carbonates include Winnofil from Solvay. TM SPM and Ultra-pflex from Silicon Motion Technology (SMI) TM and Ultra-pflex TM 100.

[0136] When (H) filler includes a thermally conductive filler, (H) filler can be both thermally conductive and electrically conductive. Alternatively, (H) filler can be thermally conductive and electrically insulating. The thermally conductive filler can also have other beneficial properties, such as but not limited to reinforcing filler, volume-increasing filler, or another property as described above. The thermally conductive filler can be selected from but not limited to the group consisting of: aluminum nitride, aluminum oxide, aluminum trihydrate, hydrous aluminum oxide, barium titanate, barium sulfate, beryllium oxide, carbon fiber, diamond, graphite, magnesium hydroxide, magnesium oxide, basic magnesium sulfate fiber, metal particles, onyx, silicon carbide, tungsten carbide, zinc oxide, coated fillers and combinations thereof.

[0137] When (H) the filler includes a thermally conductive filler, the thermally conductive filler may include a metal filler, an inorganic filler, a fusible filler, or a combination thereof. Metal fillers include metal particles, metal powders, and metal particles having a layer on the surface of the particles. These layers may be, for example, metal nitride layers or metal oxide layers. Examples of suitable metal fillers include particles of metals selected from the group consisting of aluminum, copper, gold, nickel, silver, and combinations thereof, and alternatively aluminum. Examples of suitable metal fillers also include particles of the metals listed above having layers on their surfaces, which are selected from the group consisting of aluminum nitride, aluminum oxide, copper oxide, nickel oxide, silver oxide, and combinations thereof. For example, the metal filler may include aluminum particles having an aluminum oxide layer on their surfaces. Examples of inorganic fillers include onyx; aluminum trihydrate, aluminum hydroxide, metal oxides (such as aluminum oxide, beryllium oxide, magnesium oxide, and zinc oxide); nitrides (such as aluminum nitride); carbides (such as silicon carbide and tungsten carbide); and combinations thereof. Alternatively, examples of inorganic fillers include aluminum oxide, zinc oxide, and combinations thereof. The fusible filler may include Bi, Ga, In, Sn or their alloys. The fusible filler may optionally further include Ag, Au, Cd, Cu, Pb, Sb, Zn or a combination thereof. Examples of suitable fusible fillers include Ga, In-Bi-Sn alloys, Sn-In-Zn alloys, Sn-In-Ag alloys, Sn-Ag-Bi alloys, Sn-Bi-Cu-Ag alloys, Sn-Ag-Cu-Sb alloys, Sn-Ag-Cu alloys, Sn-Ag alloys, Sn-Ag-Cu-Zn alloys and combinations thereof. The melting point of the fusible filler may be 50° C. to 250° C. The fusible filler may be a eutectic alloy, a non-eutectic alloy or a pure metal. Many suitable fusible fillers are commercially available.

[0138] Alternatively or in addition, the (H) filler may comprise a non-reactive silicone resin other than component (A). For example, the (H) filler may comprise a T resin, a TD resin, a TDM resin, a TDMQ resin, or any other non-reactive silicone resin. Typically, such non-reactive silicone resins comprise at least 30 mol % of T siloxy and / or Q siloxy units. As is known in the art, the D siloxy units consist of R 0 2SiO 2 / 2 Represented by, and T siloxy unit is composed of R 0 SiO 3 / 2 Indicates that R 0 are independently selected substituents.

[0139] Weight average molecular weight M of non-reactive silicone resin w The molecular weight of the silicone resin will depend at least in part on the type of substituents (e.g., hydrocarbon groups) present in the non-reactive silicone resin. wrepresents the weight average molecular weight measured using conventional gel permeation chromatography (GPC), calibrated using narrow molecular weight distribution polystyrene (PS) standards when the peak representing the neopentamer is excluded from the measurement. PS equivalent weight M of non-reactive silicone resin w It can be 12,000 g / mole to 30,000 g / mole, typically 17,000 g / mole to 22,000 g / mole. The non-reactive silicone resin can be prepared by any suitable method. This type of silicone resin has been prepared by co-hydrolysis of the corresponding silane or by a silica hydrosol end-capping method generally known in the art.

[0140] Phosphor is a filler of this type, which can convert the emission wavelength from a light source (optical semiconductor device) when the cured product of the composition is used as a wavelength conversion material. Such phosphors are not particularly limited, and examples of phosphors include yellow, red, green and blue phosphors, including oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, etc., which are widely used in light emitting diodes (LEDs).

[0141] In certain embodiments, (H) filler may include an acid acceptor. Acid acceptors may include metal oxides, such as magnesium oxide. Acid acceptors are generally known in the art and are commercially available under trade names including Rhenofit F, Star Mag CX-50, Star MagCX-150, BLP-3, and MaxOx98LR. Rhenofit F is calcium oxide purchased from Rhein Chemie Corporation in Shaden, Ohio, USA. Star Mag CX-50 is magnesium oxide purchased from Merrand International Corp. in Portsmouth, New Hampshire, USA. MagOX98LR is magnesium oxide purchased from Premier Chemicals LLC in West Conshohocken, Pennsylvania, USA. BLP-3 is calcium carbonate purchased from Omya Americas in Cincinnati, Ohio, USA.

[0142] Regardless of the choice of (H) filler, the (H) filler may be untreated, pretreated, or added to form the composition with an optional filler treating agent which, when so added, treats the (H) filler in situ in the composition.

[0143] The filler treating agent may include a silane (such as an alkoxysilane), an alkoxy functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl functional oligosiloxane (such as dimethylsiloxane or methylphenylsiloxane), an organosilicon compound, a stearate, or a fatty acid. The filler treating agent may include a single filler treating agent, or a combination of two or more filler treating agents selected from similar or different types of molecules.

[0144] The filler treatment agent may include an alkoxysilane, which may be a monoalkoxysilane, a dialkoxysilane, a trialkoxysilane, or a tetraalkoxysilane. Examples of alkoxysilane filler treatment agents are: hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenyltrimethoxysilane, phenethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof. In certain aspects, the alkoxysilane may be used in combination with a silazane, which may catalyze the reaction of a less reactive alkoxysilane with a surface hydroxyl group. Such reactions are typically performed at temperatures above 100°C with high shear forces and with the removal of volatile byproducts such as ammonia, methanol, and water.

[0145] Suitable filler treating agents also include alkoxysilyl functionalized alkylmethylpolysiloxanes, or similar materials where the hydrolyzable groups may include, for example, silazane, acyloxy, or oxime groups.

[0146] Alkoxy functional oligosiloxanes can also be used as filler treating agents. Alkoxy functional oligosiloxanes and methods for their preparation are well known in the art. Other filler treating agents include mono-terminated alkoxy functional polydiorganosiloxanes, i.e., polyorganosiloxanes having alkoxy functionality at one end.

[0147] Alternatively, the filler treating agent can be any organosilicon compound commonly used to treat silica fillers. Examples of organosilicon compounds include organochlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane; organosiloxanes such as hydroxyl-terminated dimethylsiloxane oligomers, silhydride functionalized siloxanes, hexamethyldisiloxane, and tetramethyldivinyldisiloxane; organosilazanes such as hexamethyldisilazane and hexamethylcyclotrisilazane; and organoalkoxysilanes such as alkylalkoxysilanes having methyl, propyl, n-butyl, isobutyl, n-hexyl, n-octyl, isooctyl, n-decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl substituents. The organic reactive alkoxysilane may include amino, methacryloxy, vinyl, glycidoxy, epoxycyclohexyl, isocyanurate, isocyanate, mercapto, thio, vinyl-benzyl-amino, benzyl-amino, or phenyl-amino substituents. Alternatively, the filler treatment agent may include an organopolysiloxane. Using such a filler treatment agent to treat the surface of the (H) filler can utilize multiple hydrogen bonds (clustered or dispersed or both) as a method for bonding the organosiloxane to the surface of the (H) filler. The organosiloxane capable of hydrogen bonding has an average of at least one silicon-bonded group capable of hydrogen bonding per molecule. The group may be selected from: a monovalent organic group having multiple hydroxyl functional groups or a monovalent organic group having at least one amino functional group. Hydrogen bonding may be the main mode of bonding of the organosiloxane to the (H) filler. The organosiloxane may not be able to form a covalent bond with the (H) filler. The organosiloxane capable of hydrogen bonding may be selected from the group consisting of: a sugar-siloxane polymer, an amino-functionalized organosiloxane, and a combination thereof. Alternatively, the polyorganosiloxane capable of hydrogen bonding may be a sugar-siloxane polymer.

[0148] Alternatively, the filler treatment agent may include alkyl mercaptans (such as octadecyl mercaptan, etc.) and fatty acids (such as oleic acid, stearic acid), titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof. Those skilled in the art can optimize the filler treatment agent to help (H) filler dispersion without undue experimentation.

[0149] If used, the relative amounts of filler treating agent and (H) filler are selected based on the specific filler used as well as the filler treating agent and their desired effects or properties.

[0150] The amount of component (H) is not limited, but when used, the composition generally contains component (H) in an amount of 10 to 2,000 parts by mass, alternatively 10 to 1500 parts by mass, alternatively 10 to 1000 parts by mass, relative to the sum of components (A) to (D) (100 parts by mass).

[0151] In certain embodiments, the composition further comprises an inhibitor. The inhibitor can be used to change the reaction rate or curing rate of the composition compared to a composition comprising the same starting material but omitting the inhibitor. The inhibitor is exemplified by alkynols, such as methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyne-3-ol, and 1-ethynyl-1-cyclohexanol and combinations thereof; cycloalkenyl siloxanes, such as methyl vinyl cyclosiloxanes, which are exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxanes. oxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and combinations thereof; ene-yne ​​compounds, such as 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne; triazoles, such as benzotriazole; phosphines; thiols; hydrazines; amines, such as tetramethylethylenediamine; fumaric acid dialkyl esters, fumaric acid dienyl esters, fumaric acid dialkoxyalkyl esters; maleic acid esters, such as maleic acid diallyl ester; nitriles; ethers; carbon monoxide; olefins, such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols, such as benzyl alcohol; and combinations thereof. Alternatively, the inhibitor may be selected from the group consisting of alkynols (eg, 1-ethynyl-1-cyclohexanol) and maleates (eg, diallyl maleate, bismaleate or n-propyl maleate) and combinations of two or more thereof.

[0152] Alternatively, the inhibitor may be a silylated acetylenic compound. Without wishing to be bound by theory, it is believed that the addition of a silylated acetylenic compound reduces the yellowing of the reaction product prepared by the hydrosilylation reaction of the composition compared to the reaction product obtained by the hydrosilylation of the composition not comprising a silylated acetylenic compound or comprising an organic acetylenic alcohol inhibitor such as those described above.

[0153] Examples of silylated acetylenic compounds are (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane. 1-Hexyne-3-oxy)trimethylsilane, (3-phenyl-1-butyne-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyne-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyne-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyne-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethynyl-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethynyl-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethynyl-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethynyl-1-oxy)trimethylsilane, and combinations thereof. Alternatively, the inhibitor is exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane or a combination thereof. Silylated acetylenic compounds useful as inhibitors may be prepared by methods known in the art, such as by reacting the above acetylenic alcohols with chlorosilanes in the presence of an acid acceptor to silylate the above acetylenic alcohols.

[0154] The amount of inhibitor present in the composition will depend on various factors, including the desired pot life of the composition, whether the composition will be a one-component or multi-component composition, the specific inhibitor used, and the selection and amounts of components (A) to (D). However, when present, the amount of inhibitor (D) may be 0% to 1%, alternatively 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%, based on the total weight of the composition.

[0155] The composition may also include (K) an organopolysiloxane or an organosiloxane oligomer in addition to component (A), wherein the (K) organopolysiloxane or organosiloxane oligomer does not include hydrosilylation reactive functional groups. As known in the art, hydrosilylation reactive functional groups are silicon-bonded organic groups having aliphatic unsaturated groups (i.e., alkenyl and alkynyl groups) and silicon-bonded hydrogen atoms. When used, component (K) may be an oligomer, a polymer, a partially branched polymer, a branched polymer, or a three-dimensional network (i.e., a resin). Component (K) may include any combination of M, D, T, and Q siloxy units. If used, component (K) does not participate in the hydrosilylation reaction to cure the composition and obtain a cured product, i.e., an organosilicon gel, as does component (A).

[0156] In certain embodiments, the composition comprises an organopolysiloxane having a hydrosilylation-reactive functional group other than components (B)-(D) in an amount of less than 10 wt%, alternatively less than 9.5 wt%, alternatively less than 9.0 wt%, alternatively less than 8.5 wt%, alternatively less than 8.0 wt%, alternatively less than 7.5 wt%, alternatively less than 7.0 wt%, alternatively less than 6.5 wt%, alternatively less than 6.0 wt%, alternatively less than 5.5 wt%, alternatively less than 5.0 wt%, alternatively less than 4.5 wt%, alternatively less than 4.0 wt%, alternatively less than 3.5 wt%, alternatively less than 3.0 wt%, alternatively less than 2.5 wt%, alternatively less than 2.0 wt%, alternatively less than 1.5 wt%, alternatively less than 1.0 wt%, alternatively less than 0.5 wt%, alternatively 0 wt%, based on the total weight of the composition.

[0157] In some embodiments, the composition further comprises a heat resistance improver in addition to component (G). Other resistance improvers are exemplified by iron oxide (red iron oxide), cerium oxide, cerium dimethylsilanol, fatty acid cerium salt, cerium hydroxide, zirconium compounds, copper (Cu) phthalocyanine, or a combination thereof.

[0158] In some embodiments, the composition further comprises one or more additives. Examples of suitable additives that may be present in the composition include fillers, treating agents (e.g., filler treating agents), crosslinking agents, adhesion promoters, surface modifiers, desiccants, compatibilizers, biocides, flame retardants, plasticizers, end-capping agents, binders, anti-aging additives, water release agents, pigments, dyes, rheology modifiers, carriers, tackifiers, corrosion inhibitors, catalyst inhibitors, viscosity modifiers, UV absorbers, antioxidants, light stabilizers, etc., and combinations thereof.

[0159] In certain embodiments, the composition and the silicone gel formed by curing the composition are substantially transparent.

[0160] The composition can be cured to obtain a cured product in the form of a silicone gel having excellent physical properties, including resistance to cracking when exposed to elevated temperatures for extended periods of time. The silicone gel has excellent bonding properties to electrical or electronic parts because the occurrence of bubbles and cracks can be suppressed.

[0161] The cured product or silicone gel typically has a Shore 000 hardness of 10 to 100, alternatively 50 to 90, alternatively 70 to 90. Shore 000 hardness can be measured according to ASTM D2240.

[0162] The composition is typically cured by exposing the composition to an elevated temperature. The elevated temperature is not particularly limited, but is typically 60°C to 150°C, alternatively 70°C to 130°C. Alternatively, the composition may be cured at ambient conditions such as room temperature, i.e., without exposing the composition to an elevated temperature.

[0163] The silicone gel has excellent heat resistance at high temperatures of 180°C and above, and the silicone gel does not tend to deteriorate when used for a long time at high temperatures. In addition, when used in applications to protect electronic components such as semiconductor chips, SiC semiconductor chips, ICs, hybrid ICs, and power devices, the occurrence of bubbles and cracks in the silicone gel can be suppressed even under high temperature conditions, and further, because the silicone gel has good adhesion to electrical or electronic parts, the silicone gel has the advantage of being able to provide electrical or electronic parts with high reliability and stability. In addition, because the silicone gel of the present invention is transparent, light-emitting semiconductor elements such as LEDs can be included in the above-mentioned semiconductor chips. Therefore, the silicone gel is particularly suitable for use as an encapsulant for electronic products.

[0164] The method for sealing or filling an electric or electronic part with the composition to form an encapsulant for the electric or electronic part is not limited, but one example is to bring a portion of the electric or electronic part to be protected into contact with the composition and then cure it by heating it, allowing it to stand at room temperature, or irradiating it with ultraviolet rays, thereby obtaining an electric or electronic part with an encapsulant, which is a silicone gel formed from the composition.

[0165] The electric or electronic parts sealed, filled or encapsulated by the silicone gel of the present invention are not limited, but because the silicone gel of the present invention can suppress the occurrence of bubbles and cracks even under high temperature conditions and show good adhesion to the electric or electronic parts, it can be advantageously used in power devices used under high temperature conditions, particularly power devices such as motor control, motor control for transportation, power generation systems or space transportation systems. In addition, because the silicone gel of the present invention has a certain degree of cold resistance in addition to the heat resistance required in SiC semiconductor chips (for example, heat resistance of 180° C. or higher), it can be advantageously used in power devices that require the ability to withstand a sharp temperature difference, and the durability and reliability of such power devices can be improved. Examples of such power devices requiring heat resistance and cold resistance include motor control used in cold areas such as general inverter control, servo motor control, motor control of machine tools or elevators, electric vehicles, hybrid vehicles or railway transportation used in cold areas, power generation systems used in cold areas such as solar, wind or fuel cell generators, space transportation systems used in space, and the like. A "cold area" is an area where the temperature falls below 0° C. In addition, the encapsulant for electrical or electronic parts of the present invention is also effective in electrical or electronic parts having a structure in which the space between electrodes, between electrical components, or between electrical components and packaging in the electrical or electronic parts is narrow, or having a structure in which these structures cannot track the expansion and contraction of the silicone gel. For example, it can be used for circuits or modules on which electrical components such as semiconductor components, capacitors and resistors are mounted, i.e., various sensors such as pressure sensors that are usually sealed or filled with silicone, as well as automobile ignition, regulators, etc. The electronic product can be an optoelectronic device, and the electronic product can be mounted on, for example, a general lighting device, an advertising display product, an optical product, or an optoelectronic product.

[0166] Examples of such electric or electronic parts are the same as those described above, particularly power devices such as motor controls, motor controls for transportation, power generation systems or space transportation systems.

[0167] The semiconductor chip protection method according to the present invention is a method for protecting a semiconductor chip by using the silicone gel of the present invention, and an example thereof is a semiconductor chip protection method using the sealant for an electric or electronic part of the present invention as a sealant. By this semiconductor chip protection method, an electric or electronic part, particularly a power device, having high reliability and stability even under high temperature conditions can be provided because it uses the silicone gel of the present invention.

[0168] The following examples are intended to illustrate the present invention and should not be viewed in any way as limiting the scope of the present invention.

[0169] Certain components utilized in the examples are listed in Table 1 below.

[0170] Table 1: Components / compounds used :

[0171]

[0172]

[0173] Preparation Example 1

[0174] A three-necked round bottom flask equipped with a stirring mechanism, a nitrogen purge, a thermocouple and a water-cooled condenser is provided. The organopolysiloxane resin linear mixture is prepared by mixing 50.6 parts by weight of an organopolysiloxane resin (A1) and 49.4 parts by weight of a linear organopolysiloxane (B1) in a flask. The organopolysiloxane resin linear mixture is heated to 80°C and blended until a uniform mixture is formed. The uniform mixture is cooled to room temperature and then transferred to the addition funnel of a wiped film evaporator. The jacket of the wiped film evaporator is heated to 150°C and a suction vacuum of <1 mmHg is applied. The rotor blades of the wiped film evaporator are then turned on, and the uniform mixture is gradually fed through the wiped film evaporator via metered addition. The volatiles are then discarded and the non-volatiles are collected. The collected non-volatiles are referred to as MQ blends. The MQ blends contained a volatile matter content of less than 2 wt. %, and in particular less than 0.3 wt. % of the QM4 neopentamer, as confirmed by GC analysis.

[0175] General Procedure 1: Examples 1-5

[0176] The compositions of Examples 1-5 were prepared according to General Procedure 1. In General Procedure 1, a dynamic axial centrifuge (DAC mixer) and a plastic container compatible therewith were provided. The following intermediates were loaded into a plastic container in the specified amounts (as shown in the table below): MQ blend, Q-branched organopolysiloxane (D1) and linear organohydrogenpolysiloxane (C1). The intermediates were then mixed in a DAC mixer at 2,000 revolutions per minute (RPM) for 30 seconds. The walls of the plastic container were then scraped to remove the intermediates from the walls. The mixing steps were repeated until a uniform blend was obtained. The hydrosilylation reaction catalyst (E1) was then added to the plastic container and mixed with the other intermediates in a DAC mixer at 2,000 RPM for 30 seconds. The mixing steps were repeated until a uniform blend was obtained to obtain a curable silicone-based gel composition.

[0177] General Procedure 2: Examples 6-7

[0178] The compositions of Examples 6-7 were prepared according to General Procedure 2. In General Procedure 2, a dynamic axial centrifuge (DAC mixer) and a plastic container compatible therewith were provided. The following intermediates were loaded into a plastic container in the specified amounts (as shown in the table below): MQ blend, Q-branched organopolysiloxane (D1) and linear organohydrogenpolysiloxane (C1). The intermediates were then mixed at 2,000 RPM for 30 seconds in a DAC mixer. The walls of the plastic container were then scraped to remove the intermediates from the walls. The mixing steps were repeated until a uniform blend was obtained. Adhesion promoter (F1), thermal stabilizer (G1) and hydrosilylation catalyst (E1) were then added to the plastic container and mixed with other intermediates in a DAC mixer at 2,000 RPM for 30 seconds. The mixing steps were repeated until a uniform blend was obtained to obtain a curable silicone-based gel composition.

[0179] Table 2: Compositions of Examples 1-4

[0180]

[0181] Table 3: Compositions of Examples 5-7

[0182]

[0183]

[0184] General Procedure 3: Comparative Examples 1-4

[0185] The compositions of Comparative Examples 1-4 were prepared according to General Procedure 3. In General Procedure 3, a dynamic axial centrifuge (DAC mixer) and a plastic container compatible therewith were provided. The following intermediates were loaded into a plastic container in a specified amount (as shown in Table 4 below): optional comparative siloxane (X1), optional comparative siloxane (X2), optional MQ blends, Q-branched organopolysiloxane (D1) and linear organohydrogenpolysiloxane (C1). The intermediates were then mixed at 2,000RPM for 30 seconds in a DAC mixer. The walls of the plastic container were then scraped to remove the intermediates from the walls. The mixing steps were repeated until a uniform blend was obtained. The hydrosilylation reaction catalyst (E1) was then added to the plastic container and mixed with other intermediates at 2,000RPM for 30 seconds in a DAC mixer. The mixing steps were repeated until a uniform blend was obtained to obtain a comparative curable silicone-based gel composition.

[0186] Table 4: Compositions of Comparative Examples 1-4

[0187]

[0188]

[0189] The compositions of Examples 1-7 and Comparative Examples 1-4 were cured to obtain cured silicone gels, and analyzed as described below.

[0190] Curing and thermal stability testing

[0191] The compositions of Examples 1-7 and Comparative Examples 1-4 were mixed on a DAC mixer at 500 RPM for 30 seconds to eliminate any bubbles. For each composition, a 20 g aliquot was carefully poured into a clean and dry Pyrex TM Petri dishes and seven 10 g aliquots were carefully poured into clean Al Petri dishes. Each composition was cured for 48 hours at ambient conditions (22° C. and 48% relative humidity) on a horizontal surface to give a cured gel.

[0192] Initial (T0) observations of the cured gel were collected. Shore 000 hardness was measured according to ASTM D2240, and the cured gel was inspected for clarity and the presence of any cracks, bubbles or other defects. The cured gel samples in the Al petri dish were placed in a 150°C convection oven and the Pyrex TM The cured gel samples in the Petri dish were placed on a hot plate with a surface temperature of 200°C. The samples were monitored regularly during the study: the samples were tested for Shore 000 hardness and observed for cracks, bubbles and other defects; photos were captured using a camera and are shown in Figures 1 to 3 , which illustrates the cured gels of Examples 1-7 and Comparative Examples 1-3 initially and after 744 hours of heat aging. The thermal stability study was conducted for a period of 744 hours (31 days).

[0193] Rheological test methods

[0194] Rheological data were obtained using an Anton Paar MCR-302 rheometer. Gel curing and rheological testing were performed at 25°C using 25 mm parallel plates. The previously cured gel was mixed on a DAC mixer at 500 rpm for 30 seconds to eliminate bubbles. An aliquot was loaded onto the rheometer. Curing of the gel formulation was ensured by monitoring the viscoelastic properties; once the gel formulation was cured, the viscoelastic properties did not show significant changes. Then, a viscoelastic data set was obtained at 1 Hz by applying strain in the linear viscoelastic region.

[0195] The results of the thermal stability tests summarized in Tables 5 to 7 below indicate that Examples 1-7 have better thermal stability than Comparative Examples 1-3. Unlike the cured gels of Examples 1-7, the cured gels of Comparative Examples 1-3 failed the thermal stability test and showed crack formation by the 744 hour mark in the following cases: the MQ blend was replaced with comparative siloxane (X1) as in Comparative Example 1; the organopolysiloxane (A2) was eliminated as in Comparative Example 2; or the organopolysiloxane (A2) was less than 3 wt% loading as in Comparative Example 3. In Tables 5 to 7 below, T0 indicates the mass of the gel when formed (i.e., at time zero), and T744hr indicates the mass of the gel after aging for 744 hours at 200° C. on a hot plate.

[0196] The damping properties were evaluated using a rheological property, Tan δ. Tan δ represents the ratio of the viscous response to the elastic response of a material (G" / G'), or the energy dissipation potential of a material. The larger the Tan δ value, the higher the damping properties. The rheological properties are summarized in Tables 5 to 7 below. The addition of the organopolysiloxane resin (A2) systematically improved the damping properties; as the content of the organopolysiloxane resin (A2) increased from 3 wt% to 20 wt%. As shown in Comparative Example 3 and Examples 1-5, the Tan δ value increased from 0.10 to 0.19. Comparative Example 4 has 25 wt% of comparative siloxane (X2) as a non-functional component, while Example 5 has a comparable content (20 wt%) of non-functionalized MQ resin (i.e., organopolysiloxane resin (A2)). Despite the addition of comparable non-functional components, the Tan δ value of Example 5 is higher than the Tan δ value of Comparative Example 4 without any significant loss in G'.

[0197] Table 5: Properties of Examples 1-4

[0198] Measurement / Observation standard Example 1 Example 2 Example 3 Example 4 Gel quality - T0 No cracks qualified qualified qualified qualified Gel Quality - T744hr No cracks qualified qualified qualified qualified Shaw 000-T0 N / A 80.4 76.8 78.4 76.2 Shaw 000-T744hr N / A 75.0 79.6 75.2 73.6 Shore 000 Change % <+5％ -6.7％ 3.6％ -4.1％ -3.4％ G'[Pa] N / A 36,843 35,705 33,663 30,996 G”[Pa] >3,000 3,788 4,061 4,218 4,294 Tanδ[-] ≥0.10 0.10 0.11 0.13 0.14

[0199] Table 6: Properties of Examples 5-7

[0200] Measurement / Observation standard Example 5 Example 6 Example 7 Gel quality - T0 No cracks qualified qualified qualified Gel Quality - T744hr No cracks qualified qualified qualified Shaw 000-T0 N / A 75.6 78.2 79.0 Shaw 000-T744hr N / A 73.4 76.8 79.0 Shore 000 Change % <+5％ -2.9％ -1.8％ 0.0％ G'[Pa] N / A 24,104 36,187 31,633 G”[Pa] >3,000 4,501 3,991 3,957 Tanδ[-] ≥0.10 0.19 0.11 0.13

[0201] Table 7: Properties of Comparative Examples 1-4

[0202] Measurement / Observation standard Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Gel quality - T0 No cracks qualified qualified qualified qualified Gel Quality - T744hr No cracks Failure Failure Failure qualified Shaw 000-T0 N / A 77.2 68.0 82.2 74.2 Shaw 000-T744hr N / A 86.8 73.4 78.6 73.4 Shore 000 Change % <+5％ 12.4％ 7.9％ -4.4％ -1.1％ G'[Pa] 70,622 10,205 38,633 24,570 G”[Pa] >3,000 4,104 2,020 3,635 2,203 Tanδ[-] >0.10 0.06 0.20 0.09 0.09

Claims

1. A curable silicone-based gel composition, comprising: (A) an organopolysiloxane resin having a mass loss of 2.0% by mass or less when component (A) is exposed to 200° C. for 1 hour and represented by the following formula: (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e Each R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturation in the group; each R 2 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a, b, c, d and e are numbers satisfying the following conditions: 0.10≤a≤0.60, 0.0≤b≤0.70, 0.0≤c≤0.80, 0.10≤d≤0.65, 0≤e≤0.05, and a+b+c+d=1; (B) a linear organopolysiloxane having two silicon-bonded alkenyl groups only at its molecular terminals and represented by the following formula: (R 3 R 1 2SiO 1 / 2 )(R 1 2SiO 2 / 2 ) n (R 3 R 1 2SiO 1 / 2 ) Each R 1 are independently selected and defined above; each R 3 is independently an alkenyl group having 2 to 10 carbon atoms; and subscript n is a number from 10 to 1000; (C) a linear organohydrogenpolysiloxane having only two silicon-bonded hydrogen atoms at its molecular terminals and having a viscosity at 25° C. of 2 MPa·s to 10,000 MPa·s; (D) a Q-branched organopolysiloxane having at least three silicon-bonded alkenyl groups at the molecular terminals thereof and represented by the following formula: (SiO 4 / 2 )[(R 1 2SiO 2 / 2 ) m (R 4 3SiO 1 / 2 )]4 Each R 1 are independently selected and defined above; each R 4 Independently for R 1 or an alkenyl group having 2 to 10 carbon atoms, provided that R 4 At least three of are alkenyl groups; and each subscript m is independently a number from 5 to 200; and (E) A hydrosilylation reaction catalyst in an amount sufficient for the curing reaction in components (A) to (D).

2. The curable silicone-based gel composition according to claim 1, wherein when the total mass of components (A) to (E) in the composition is 100 mass%, the amount of component (A) is in the range of 5 mass% to 25 mass%, The amount of component (B) is in the range of 5% to 50% by mass, The amount of component (C) is in the range of 5% to 25% by mass, The amount of component (D) is in the range of 30% to 80% by mass, and The amount of component (E) is 0.001% by mass to 1.0% by mass in terms of platinum group metal.

3. The curable silicone-based gel composition according to claim 1 or claim 2, further comprising at least one selected from the group consisting of: (F) an adhesion promoter; or (G) (g1) an alkali metal silane alkoxide and (g2) selected from M 1 Cl y Chloride salt represented by (R 5 COO y M 1 represents the reaction product of at least one salt of a carboxylate, wherein each R 5 are the same or different monovalent hydrocarbon groups, M 1 is cerium or a rare earth metal mixture containing cerium as a main component, y depends on M 1 The valence of is in the range of 1 to 3; The amount of component (F) or component (G) is 0.001% by mass to 2.0% by mass relative to the total mass of components (A) to (E) in the composition as 100% by mass.

4. The curable silicone-based gel composition according to any preceding claim, further comprising at least one selected from the group consisting of: (H) an inorganic filler, which is optionally treated with at least one surface treatment agent and / or is optionally mixed with other components; (I) pigments; or (J) an organopolysiloxane or an organosiloxane oligomer different from component (A), wherein the organopolysiloxane or organosiloxane oligomer of component (K) does not include a hydrosilylation-reactive functional group containing an aliphatic unsaturated group in the molecule.

5. The curable silicone-based gel composition according to any preceding claim, comprising 0.0% by mass to 10.0% by mass of an organopolysiloxane having a hydrosilylation-reactive functional group other than components (B) to (D), relative to the total mass content of components (A) to (E) in the composition as 100% by mass. 6 . An encapsulant for electronic products, the encapsulant comprising the curable silicone-based gel composition according to claim 1 .

7. The encapsulant for electronic products according to claim 6, which is substantially transparent.

8. A silicone-based gel prepared by curing the curable silicone-based gel composition according to any one of claims 1 to 5, the silicone-based gel having a Shore 000 hardness ranging from 10 to 100.

9. The silicone-based gel of claim 8, being substantially transparent. 10 . An electronic product comprising the encapsulant according to claim 6 or claim 7 or the silicone-based gel according to claim 8 or claim 9 . The electronic product according to claim 10 , wherein the electronic product is mounted on a power device.

12. The electronic article of claim 10, wherein the electronic article is an optoelectronic device.

13. The electronic product according to claim 12, wherein the electronic product is mounted on a general lighting device, a display product, an optical product or an optoelectronic product.

14. A protection method for semiconductor chips, characterized by using the curable silicone-based gel composition according to any one of claims 1 to 5, the encapsulant according to claim 6 or claim 7, or the silicone-based gel according to claim 8 or claim 9.

Images