Curable silicone composition
A dual-curable silicone composition, featuring a combination of alkenyl-functional and silyl-hydride functional polyorganosiloxanes along with a silane terminated polyether and appropriate catalysts, addresses the issue of cure inhibition by soldering fluxes, achieving complete curing and maintaining the encapsulant's modulus.
Patent Information
- Application Number
- PCT/CN2023/131919
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-11-16
- Publication Date
- 2025-05-22
AI Technical Summary
Existing curable silicone compositions used as encapsulants or sealants in electronic devices are susceptible to cure inhibition by soldering fluxes, leading to incomplete curing and adverse effects on the modulus of the resulting encapsulants.
A dual-curable silicone composition comprising an alkenyl-functional polyorganosiloxane, a silyl-hydride functional polyorganosiloxane, a silane terminated polyether, a hydrosilation reaction catalyst, and a condensation reaction catalyst, which cures through both hydrosilylation and condensation reactions, providing superior inhibition resistance against soldering fluxes.
The dual-curable silicone composition effectively resists cure inhibition by soldering fluxes, ensuring complete curing and maintaining the desired modulus of the encapsulants, even when in contact with room temperature dried soldering fluxes.
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Figure PCTCN2023131919-FTAPPB-I100001 
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Figure PCTCN2023131919-FTAPPB-I100003
Abstract
Description
CURABLE SILICONE COMPOSITIONFIELD
[0001] The present invention relates to a curable silicone composition and an electric or electronic device comprising a cured product of such composition. Particularly, the present invention relates to a hydrosilation and condensation dual-curable composition that cure to form a silicone sealant or encapsulant with superior inhibition resistance.
[0002] INTRODUCTION
[0003] Electric devices that are planted in modules need to tolerate various stresses, including, for example, shock, dirt and moisture. Silicone encapsulants are widely used for electric circuit protection with direct contact with electric circuits and module cases, which are more secure than merely module cases, sealants and conformal coatings, especially when the modules are applied outdoor. Addition curable (i.e., curable via a hydrosilylation reaction) silicone compositions are widely used as encapsulants with many advantages such as easily tuned curing speed and modulus etc. These addition curable compositions typically comprise an alkenyl-functional polyorganosiloxane, a silyl-hydride functional polyorganosiloxane, and a platinum-based hydrosilylation reaction catalyst. Unfortunately, addition cure tends to be influenced by the environment. Some contaminants, impurities, or even the bulky components of the substrate may decrease the cure speed of hydrosilylation or even prevent the curing from taking place. Such effect is usually referred to as “inhibition of cure. ” During manufacturing of electric circuits, it is the trend in the electronic assembly industry (particularly, microelectronic industry) to use no-clean fluxes in trying to eliminate the need for a cleaning process to remove flux residues after a soldering process, due to the environmental and health concerns, complexities and difficulties associated with the cleaning process. However, flux residues often inhibit the addition cure of polyorganosiloxane compositions, which has adverse impacts on the modulus of the obtained encapsulants and may even lead to non-cure of the polyorganosiloxane compositions when contact with soldering fluxes. Incorporation of condensation curable alkoxyl-terminated siloxanes or alkoxysilyl-containing polyorganosiloxanes having alkenyl groups into the addition curable polyorganosiloxane compositions can provide dual-cured products with improved adhesion to substrates, but the ability of the resultant composition to resist the cure inhibition caused by flux residues is limited, particularly when excess flux spatters on circuits boards or spreads excessively without subsequent high-temperature (e.g., 150 degrees Celsius or higher) baking. For example, when such composition cures in contact with room temperature dried soldering fluxes, lots of uncured fluids have been observed at the interface.
[0004] There remains a need to identify a curable silicone composition particularly suitable for use as encapsulants or sealants and affording inhibition resistance against soldering fluxes.SUMMARY
[0005] The present invention provides a novel curable silicone composition (also referred to as “curable composition” ) comprising a specific combination of an alkenyl-functional polyorganosiloxane, a silyl-hydride functional polyorganosiloxane, a specific amount of a specific silane terminated polyether, a hydrosilation reaction catalyst, and a condensation reaction catalyst. Such curable composition is a dual curable composition, that is, a hydrosilylation reaction and condensation reaction curable composition. The curable composition shows superior inhibition resistance against soldering fluxes (even room-temperature-dried soldering fluxes) that are in contact with the composition during curing, as measured according to the test method described in the Examples section below. The curable composition is particularly suitable for use as encapsulants and sealants for electric or electronic devices. Curing of the curable composition occurs via both hydrosilylation reaction and condensation reaction, thereby obtaining a hydrosilation and condensation dual-cured product.
[0006] In a first aspect, the present invention is a curable silicone composition comprising:
[0007] (A) an alkenyl-functional polyorganosiloxane having an average of at least two alkenyl groups per molecule and free of a silicon atom-bonded alkoxy group;
[0008] (B) from 0.1 to 20 weight percent, based on the weight of the alkenyl-functional polyorganosiloxane (A) , of a silyl-hydride functional polyorganosiloxane having an average of at least two silicon atom-bonded hydrogen atoms per molecule and free of an alkenyl group;
[0009] (C) from 3 to 50 weight percent, based on the weight of the alkenyl-functional polyorganosiloxane (A) , of a silane terminated polyether having at least two (R) m (Y) 3-m-Si groups per molecule, where each R is independently selected from a hydroxyl group and a hydrolysable group, each Y is independently an alkyl group having from 1 to 8 carbons, and subscript m is 1, 2, or 3;
[0010] (D) a hydrosilation reaction catalyst present in an amount sufficient to provide 1 to 1000 ppm of platinum group metal; and
[0011] (E) a condensation reaction catalyst.
[0012] In a second aspect, the present invention is an electric or electronic device comprising an electric or electronic component and a silicone material on at least one surface of the electric or electronic component, wherein the silicone material is a cured product of the curable silicone composition of the first aspect.
[0013] In a third aspect, the present invention is a method of making an electric or electronic device. The method comprises:
[0014] i) applying the curable silicone composition of the first aspect on and in contact with at least one surface of an electric or electronic component of the electric or electronic device; and
[0015] ii) curing the curable silicone composition, thereby forming a silicone material.DETAILED DESCRIPTION
[0016] Test methods refer to the most recent test method as of the priority date of this document when a date is not indicated with the test method number. References to test methods contain both a reference to the testing society and the test method number. The following test method abbreviations and identifiers apply herein: ASTM refers to ASTM International methods.
[0017] Products identified by their tradename refer to the compositions available under those tradenames on the priority date of this document.
[0018] “And / or” means “and, or as an alternative” . All ranges include endpoints unless otherwise indicated. Unless otherwise stated, all weight percent (wt%) values are relative to the weight of component (A) described herein below.
[0019] Viscosity is measured according to ASTM D 1084 Method B (for cup / spindle) and ASTM D 4287 (for cone / plate) , for example, using a rotational viscometer such as a Brookfield Synchro-electric viscometer or Brookfield Cone / Plate viscometer at 25 degrees Celsius (℃) unless otherwise stated.
[0020] Unless otherwise stated, the number average molecular weight (Mn) refers to the number average molecular weight measured using gel permeation chromatography (GPC) and the weight average molecular weight (Mw) refers to the weight average molecular weight measured using GPC. For example, a suitable GPC test method for measuring Mn and Mw is disclosed in U.S. Patent 9,593,209, Reference Example 1 at col. 31.
[0021] The curable composition of the present invention comprises components (A) , (B) , (C) , (D) and (E) , and optional components, described herein below. The curable composition comprises component (A) an alkenyl-functional polyorganosiloxane having an average of two or more alkenyl groups per molecule and free of a silicon atom-bonded alkoxy group. “Polyorganosiloxane” is a silicone polymer with repeating Si-O-Si units. “Alkenyl” means a branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon double bonds. “Monovalent hydrocarbon group” means a univalent group made up of hydrogen and carbon atoms. The alkenyl group may have 2 to 12 carbon atoms, and can have from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, or from 2 to 4 carbon atoms. Suitable alkenyl groups may include, for example, vinyl, allyl, butenyl, and hexenyl. The alkenyl groups can be terminal, pendant, or a combination of both terminal and pendant. “Terminal” groups are on end siloxane groups of a molecule. “End” siloxane groups are attached to only one other siloxane group. “Pendant” groups are on interior siloxane group -siloxane groups bound to at least two other siloxane groups -of the molecule. “Siloxane group” is a group containing SiO that is bound to another Si through the oxygen of the SiO. The alkenyl-functional polyorganosiloxane for component (A) can be a linear structure, partially branched linear structure, branched structure, cyclic structure, network structure, or dendritic structure.
[0022] The alkenyl-functional polyorganosiloxane for component (A) may have an average chemical structure (A-I) : RM(3-c) R'cSiO- (R'RMSiO) a- (RM2SiO) b-SiR'dRM (3-d) (A-I) ,
[0023] where each RM is independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, each R' is independently an alkenyl group having 2 to 12 carbon atoms, subscript a ≥ 0, subscript b > 0, subscript c is 0 or 1, subscript d is 0 or 1, (a+b) is 20 to 2,000, and (a+c+d) ≥ 2.
[0024] “Alkyl” means a cyclic, branched, or unbranched, saturated monovalent hydrocarbon group. Suitable alkyl groups for RM may include, for example, methyl, ethyl, propyl (e.g., iso-propyl 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, as well as branched saturated hydrocarbon groups of 6 carbon atoms. “Aryl” means a group containing a cyclic, fully unsaturated, hydrocarbon group. Suitable aryl groups for RM are exemplified by phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl. Each RM may be the same or different. Each RM can be independently an alkyl group. Desirably, each RM is independently methyl, ethyl, or propyl, and more desirably, each RM is methyl.
[0025] Suitable alkenyl groups for R' are as described above. Particularly suitable alkenyl groups for R' vinyl, allyl, butenyl, and hexenyl. Each R' may be the same or different. Desirably, each R' is independently selected from vinyl or hexenyl. More desirably, each R' is vinyl.
[0026] The quantity (a+c+d) is 2 or more, even 3 or more. Typically, the quantity (a+c+d) can be 30 or less, and can be 20 or less, 10 or less, or even 3 or less. Desirably, subscript a is 0, subscript c is 1, subscript d is 1, and each RM is methyl. The alkenyl-functional polyorganosiloxane for component (A) may comprise, or can consist of, one or more than one vinyldimethylsiloxy-terminated polydimethylpolysiloxane.
[0027] Subscript a is the average number of (R'RMSiO) groups per molecule. Subscript b is the average number of (RM2SiO) groups per molecule. Desirably, the quantity of (a+b) has a value sufficient to impart the alkenyl-functional polyorganosiloxane a viscosity of at 25 ℃ in a range of 20 centipoises (cP) to 20,000 cP, and can be from 30 cP to 10,000 cP, from 40 cP to 5,000 cP, or from 50 cP to 2,000 cP.
[0028] Component (A) may comprise one alkenyl-functional polyorganosiloxane of formula (A-I) or a combination of two or more alkenyl-functional polyorganosiloxanes of formula (A-I) that may differ in one or more properties such as viscosity, molecular weight, structure, siloxane units and sequence. When component (A) comprises a combination of more than one alkenyl-functional polyorganosiloxane then the viscosity is the combined viscosity of alkenyl-functional polyorganosiloxanes. Suitable alkenyl-functional polyorganosiloxanes for component (A) may comprise any one or any combination of more than one of the following polyorganosiloxanes: i) dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) dimethylvinylsiloxy-terminated poly (dimethylsiloxane / methylvinylsiloxane) , iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) trimethylsiloxy-terminated poly (dimethylsiloxane / methylvinylsiloxane) , v) trimethylsiloxy-terminated polymethylvinylsiloxane, vi) dimethylvinylsiloxy-terminated poly (dimethylsiloxane / methylvinylsiloxane) , vii) dimethylvinylsiloxy-terminated poly (dimethylsiloxane / methylphenylsiloxane) , viii) dimethylvinylsiloxy-terminated poly (dimethylsiloxane / diphenylsiloxane) , viiii) phenyl, methyl, vinyl-siloxy-terminated polydimethylsiloxane, and x) dimethylhexenylsiloxy-terminated polydimethylsiloxane. Desirably, the alkenyl-functional polyorganosiloxane is bis-vinyldimethylsiloxy-terminated polydimethylsiloxane. Methods of preparing alkenyl-functional polyorganosiloxanes, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes, are well known in the art.
[0029] Typically, the amount of component (A) the alkenyl-functional polyorganosiloxane in the curable composition may be from 5 to 90 wt%, from l0 to 80 wt%, from 20 to 70 wt%, or from 30 to 50 wt%, based on the total weight of the curable composition.
[0030] The curable composition of the present invention comprises component (B) a silyl-hydride functional polyorganosiloxane. A “silyl-hydride functional” polyorganosiloxane means a polyorganosiloxane containing a silicon atom-bonded hydrogen atom. The silyl-hydride functional polyorganosiloxane useful in the present invention has an average of at least two silicon atom-bonded hydrogen atoms, or even 3, per molecule and is free of an alkenyl group (also referred to as “SiH polymer” ) .
[0031] The silyl-hydride functional polyorganosiloxane (B) may comprise unit formula (B-I) : (RM3SiO1 / 2) p (RM2SiO2 / 2) q (RMSiO3 / 2) r (SiO4 / 2) s (RMHSiO2 / 2) t (RM2HSiO1 / 2) u (B-I) ,
[0032] where RM is described above in formula (A-I) , desirably methyl, and subscripts p, q, r, s, t, and u have values such that p≥0, q≥0, r≥0, s≥0, t≥0, u≥0, (t+u) ≥2, (p+u) ≥2, and a quantity (p+q+r+s+t+u) is sufficient to provide the silyl-hydride functional polyorganosiloxane with a degree of polymerization of 5 to 500, or l0 to 200. Degree of polymerization can be determined according to chemical structure and / or Mn of the silyl-hydride functional polyorganosiloxane.
[0033] Alternatively, the silyl-hydride functional polyorganosiloxane (B) may comprise unit formula (B-2) : (RM3SiO1 / 2) 2 (RM2SiO2 / 2) aa (RMHSiO2 / 2) bb (B-2) ,
[0034] where each RM is independently selected from the group consisting of methyl and phenyl, subscript aa is 0 to 500, and subscript bb is 5 to 50.
[0035] Alternatively, the silyl-hydride functional polyorganosiloxane (B) is a polyorganosiloxane of formula (B-3) , of formula (B-4) , or both (B-3) and (B-4) :
[0036] RM3 SiO (RM2 SiO) g (RMHSiO) hSiRM3 (B-3) ,
[0037] RM2HSiO (RM2SiO) i (RMHSiO) jSiRM2H (B-4) ,
[0038] In formulae (B-3) and (B-4) above, RM is as described above. Subscript g has an average value of 0 to 2000, subscript h has an average value of 2 to 2000, subscript i has an average value of 0 to 2000, and subscript j has an average value of 0 to 2000.
[0039] The silyl-hydride functional polyorganosiloxane (B) may comprise a silicon atom-bonded hydrogen content of 0.005 wt%to 2 wt%or 0.01 wt%to 1.0 wt%, where the silicon atom-bonded hydrogen (SiH) content ( “SiH content” ) refers to the weight percentages of the silicon atom-bonded hydrogen atoms relative to the silyl-hydride functional polyorganosiloxane weight and can be determined using Fourier Transfer Infra-Red (FTIR) spectroscopy.
[0040] Suitable silyl-hydride functional polyorganosiloxanes for use as component (B) may comprise any one or any combination of more than one of the following silyl-hydride functional polyorganosiloxanes: i) bis-dimethylhydrogensiloxy-terminated poly (dimethyl / methylhydrogen) siloxane, ii) bis-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, iii) bis-dimethylhydrogensiloxy-terminated polydimethylsiloxane, iv) bis-trimethylsiloxy-terminated poly (dimethyl / methylhydrogen) siloxane, and v) bis-trimethylsiloxy-terminated polymethylhydrogensiloxane. Methods of preparing silyl-hydride functional polyorganosiloxanes, such as hydrolysis and condensation of organohydridihalosilanes, are well known in the art, for example, see U.S. Patent 3,957,713 to Jeram et al. and U.S. Patent 4,329,273 to Hardman, et al. Silyl-hydride functional polyorganosiloxanes can also be prepared as described, for example in U.S. Patent 2,823,218 to Speier, et al., which discloses organohydrogensiloxane oligomers and linear polymers, e.g., 1, 1, 1, 3, 3-pentamethyldisiloxane; bis-trimethylsiloxy-terminated polymethylhydrogensiloxane homopolymer; bis-trimethylsiloxy-terminated poly (dimethyl / methylhydrogen) siloxane copolymer; and cyclic polymethylhydrogensiloxanes. Silyl-hydride functional polyorganosiloxanes are also commercially available, such as those available from Gelest, Inc. of Morrisville, Pennsylvania, USA, for example, HMS-H271, HMS-071, HMS-993, HMS-301, HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301 and HPM-502.
[0041] Typically, the amount of component (B) the silyl-hydride functional polyorganosiloxane in the curable composition may be from 0.1 to 20 wt%, and can be 0.1 wt%or more, 0.5 wt%or more, 1.0 wt%or more, 2.0 wt%or more, 3.0 wt%or more, 4.0 wt%or more, 5.0 wt%or more, even 7.0 wt%or more while at the same time is generally 20.0 wt%or less, and can be 18.0 wt%or less, 16.0 wt%or less, 15.0 wt%or less, 12.0 wt%or less, 10.0 wt%or less, or even 8.0 wt%or less, based on the weight of component (A) (i.e., the weight of the alkenyl-functional polyorganosiloxane described above in the curable composition) .
[0042] Alternatively, the silyl-hydride functional polyorganosiloxane (B) may be present in an amount sufficient to provide a molar ratio of the silicon atom-bonded hydrogen atoms in component (B) to the alkenyl groups in component (A) ) of 0.2 to 0.9, and can be 0.2 or more, 0.3 or more, even 0.4 or more while at the same time is 0.9 or less, 0.85 or less, 0.8 or less or even 0.7 or less, desirably 0.2 to 0.7, and more desirably 0.3 to 0.6.
[0043] The curable composition of the present invention comprises component (C) a silane terminated polyether having at least two (R) m (Y) 3-m-Si groups (also referred to as “silyl groups” ) per molecule, where each R is independently a hydroxyl (OH) group or a hydrolysable group, each Y is independently an alkyl group containing from 1 to 8 carbons, and subscript m is 1, 2 or 3. Desirably, subscript m is 2 or 3, and each R is methoxy.
[0044] The hydrolysable group can be an alkoxy group such as methoxy, ethoxy, and propoxy. Desirably, each R is independently OH or an alkoxy group having from 1 to 10 carbons, alternatively OH or an alkoxy group having from 1 to 6 carbons, alternatively OH, methoxy (OCH3) , or ethoxy (OCH2CH3) . Desirably, substituent Y is an alkyl group having 1 to 6 carbons or 1 to 4 carbons, including, for example, methyl. Each of the (R) m (Y) 3-m-Si groups may be independently selected from the group consisting of- (Y) SiOH2, - (Y) 2SiOH, -YSi (ORB) 2, -Si (ORB) 3, and - (Y) 2SiORB, where each RB is independently an alkyl group having from 1 to 8 carbons, desirably methyl; and Y is described above.
[0045] “Polyether” refers to a polymer that has a backbone (also as “polymer backbone” ) comprising one or more polyoxyalkylene segments. The polyoxyalkylene segments contain oxyalkylene units. As used herein, the term “oxyalkylene” refers to units having the structure - (O-A) -wherein O-A represents the monomeric residue of the polymerization reaction product of a C2-C4 alkylene oxide. Desirably, the silane terminated polyether has a backbone comprising recurring oxyalkylene units represented by the average formula (-CnH2a-O-) y, where subscript n is an integer ranging from 2 to 4 and subscript y is an integer ≥ 4. Desirably, subscript y is 5 or higher, 10 or higher, even 100 or higher while at the same time is 1,000 or lower, and can be 800 or lower, or even 600 or lower. The oxyalkylene units throughout the backbone can be the same or different. Examples of the oxyalkylene units include i) oxyethylene units with the structure (-OCH2CH2-) , ii) oxypropylene units with the general structure (-C3H6-O-) , such as - (OCH (CH3) CH2) -; iii) oxybutylene units with the general structure (-C4H8-O-) , such as - (OCH (C2H5) CH2) -, - (OCH2CH2CH2CH2) -, or combinations thereof; and iv) any combination of i) , ii) and iii) . The backbone of the silane terminated polyether can contain two or more different oxyalkylene units. The different oxyalkylene units can be arranged randomly to form a random polyoxyalkylene; or can be arranged in blocks to form a block polyoxyalkylene. Block polyoxyalkylene polymers have two or more neighboring polymer blocks, wherein each of the neighboring polymer blocks contain different oxyalkylene units, and each polymer block contains at least two of the same oxyalkylene units. Desirably, the backbone of the silane terminated polyether comprises or consists of oxypropylene units.
[0046] The silane terminated polyether (C) useful in the present invention may have a viscosity in a range of from 100 cP to 1,000,000 cP, and can be from 500 cP to 800,000 cP, from 1,000 cP to 500,000 cP, or from 2,000 cP to 200,000 cP, as determined according to ASTM D 4287 at 25 ℃, for example, using a Brookfield Cone / Plate viscometer.
[0047] The (R) m (Y) 3-m-Si groups may be linked to the backbone of the silane terminated polyether (also referred to as “polyether polymer backbone” ) via any suitable linkage or may be directly bonded. The backbone of the silane terminated polyether may also comprise a urethane linkage group. For example, (R) m (Y) 3-m-Si groups may be terminal groups linked to the polyether polymer backbone as follows: (R) m (Y) 3-m-Si-D- [NH-C (=O) ] k-
[0048] where R, Y and subscript m are described above; D is a divalent C2-6 alkylene group, a C2-4 alkylene group, or an ethylene or propylene group; and subscript j is 1 or 0.
[0049] Desirably, the silane terminated polyether has the following chemical structure of formula (C-I) : (R) m (Y) 3-m-Si-D- [NH-C (=O) ] k-O- [CnH2n-O] y- [C (=O) -NH] k-D-Si (Y) 3-m (R) m
[0050] where [CnH2n-O] y is the polyether polymer backbone, desirably [CH (CH3) -CH2-O] y, where subscripts n and y are described above; and R, Y, and subscripts m and k are described above.
[0051] Methods of preparing silane terminated polyethers are known in the art, for example, by modification ofpolyoxyalkylene polymers comprising recurring oxyalkylene units as described above. The polyoxyalkylene polymers usually have terminal hydroxyl groups and can readily be modified with moisture curable silyl groups, for example, by condensation reaction with an excess of alkyltrialkoxysilanes to introduce terminal alkyldialkoxysilyl groups. Alternatively, terminal modification may occur via an addition reaction. Suitable commercially available silane terminated polyethers may include, for example, MS POLYMERTM SAX350 and SAX520 available from Kaneka.
[0052] The silane terminated polyether (C) may be present in the composition in an amount of from 3 to 50 wt%, and can be 3 wt%or more, 5 wt%or more, 8 wt%or more, 10 wt%or more, 12 wt%or more, 15 wt%or more, 20 wt%or more, 23 wt%or more, 24 wt%or more, 25 wt%or more, even 30 wt%or more while at the same time is 50 wt%or less, and can be 49 wt%or less, 48.5 wt%or less, 46 wt%or less, 45 wt%or less, 42 wt%or less, or even 40 wt%or less, desirably from 24 to 48.5 wt%, more desirably from 30 to 40 wt%, based on the weight of component (A) . Too much silane terminated polyether may lead a non-fiowable composition.
[0053] The curable silicone composition of the present invention also comprises component (D) a hydrosilylation reaction catalyst. Hydrosilylation reaction catalysts are known in the art and are commercially available. Hydrosilylation reaction catalysts include platinum (Pt) group metal catalysts. Such hydrosilylation reaction catalysts can be (D-1) a metal selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium; alternatively, platinum, ruthenium, and iridium; and desirably the metal is platinum. Alternatively, the hydrosilylation reaction catalyst may be (D-2) a compound of such a metal, for example, chloridotris (triphenylphosphane) rhodium (I) (Wilkinson's Catalyst) , a rhodium diphosphine chelate such as [1, 2-bis (diphenylphosphino) ethane] dichlorodirhodium or [1, 2-bis (diethylphospino) ethane] dichlorodirhodium, chloroplatinic acid (Speier's Catalyst) , chloroplatinic acid hexahydrate, or platinum dichloride. Alternatively, the hydrosilylation reaction catalyst may be (D-3) a complex of the platinum group metal compound with an alkenyl functional polyorganosiloxane oligomer, or (D-4) the platinum group metal compound microencapsulated in a matrix or core-shell type structure. Complexes of platinum alkenyl functional polyorganosiloxane oligomers include 1, 3-diethenyl-1, 1, 3, 3-tetramethyldisiloxane complexes with platinum (Karstedt's Catalyst) . Alternatively, the hydrosilylation reaction catalyst may comprise (D-5) the complex microencapsulated in a resin matrix. The hydrosilylation reaction catalyst, particularly, the complex described above, may be microencapsulated in the resin matrix (typically, in a phenyl resin) or non-encapsulated. The resin matrix for microencapsulation can be a phenyl resin, an acrylate polymer, a polycarbonate, or other resin matrix which has a melting point less than 150 ℃to release Pt during heat curing. Two or more different catalysts that activate at different temperatures can be added such as a mixture of the complex of platinum alkenyl functional polyorganosiloxane oligomer with an encapsulated platinum catalyst. Desirably, the hydrosilylation reaction catalyst is selected from 1, 3-diethenyl-l, 1, 3, 3-tetramethyldisiloxane complex with platinum, 1, 3-diethenyl-l, 1, 3, 3-tetramethyldisiloxane complex with platinum that is encapsulated in dimethyl siloxane with phenyl silsesquioxane, or mixtures thereof. Exemplary hydrosilylation reaction catalysts are described in U.S. Patents 2,823,218 to Speier; 3,159,601 to Ashby; 3,220,972 to Lamoreaux; 3,296,291 to Chalk, et al.; 3,419,593 to Willing; 3,516,946 to Modic; 3,715,334 to Karstedt; 3,814,730 to Karstedt; 3,928,629 to Chandra; 3,989,668 to Lee, et al.; 4,766,176 to Lee, et al.; 4,784,879 to Lee, et al.; 5,017,654 to Togashi; 5,036,117 to Chung, et al.; and 5,175,325 to Brown; and EP 0 347 895 A to Togashi, et al. Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFFTM 4000 Catalyst, SYL-OFF 4500 Catalyst, and SYL-OFF 2700 Catalyst are available from Dow Silicones Corporation (SYL-OFF is a trademark of The Dow Chemical Company) .
[0054] The amount of the hydrosilylation reaction catalyst used will depend on various factors including the selection of components (A) and (B) , and their respective contents of alkenyl groups and silicon atom-bonded hydrogen atoms (SiH) , and the content of the platinum group metal in the catalyst selected, for example, the amount of the hydrosilylation reaction catalyst is sufficient to catalyze hydrosilylation reaction of SiH and alkenyl groups, alternatively the amount of the catalyst is sufficient to provide 1 part per million (ppm) to 1000 ppm, and can be 1`ppm or more, 5 ppm or more, 10 ppm or more, 20 ppm or more, even 30 ppm or more while at the same time is generally 1,000 ppm or less, and can be 500 ppm or less, 300 ppm or less, 130 ppm or less, or even 100 ppm or less, of the platinum group metal, based on the weight of component (A) . Alternatively, when the hydrosilylation reaction catalyst comprises a platinum-organosiloxane complex, the amount of hydrosilylation reaction catalyst may be 0.001 wt%to 5 wt%, 0.005 wt%to 4.0 wt%, 0.01 wt%to 2.0 wt%, or 0.1 wt%to 1.0 wt%, based on the weight of component (A) .
[0055] The curable composition also comprises component (E) a condensation reaction catalyst. The condensation reaction catalyst may be any catalyst that can catalyze the condensation reaction of hydroxyl or hydrolysable groups (such as alkoxy groups) in the silane terminated polyether. The condensation reaction catalyst may be selected from the group consisting of a titanium-based catalyst, a zirconium-based catalyst, an aluminum-based catalyst, and mixtures thereof. Suitable titanate catalysts for component (E) may include, for example, titanium alcoholates such as tetra n-butyl titanate, tetra t-butyl titanate, tetra t-butoxy titanate, tetraisopropoxy titanate, or mixtures thereof; and titanium chelates, such as diisopropoxydiethylacetoacetate titanate or 2-propanolato, tris isooctadecanoato titanate, or mixtures thereof. Suitable zirconium catalysts for component (E) may comprise, for example, zirconium alcoholates, such as zirconium tetrapropylate or zirconium tetrabutylate, and zirconium chelates such as zirconyl diacetate, zirconium tetra (acetylacetonate) , tributoxyzirconium acetylacetonate, dibutoxyzireonium bis-(acetylacetonate) , tributoxyzirconium acetoacetate, and dibutoxyzirconium acetylacetonate (ethylacetoacetate) ; or mixtures thereof. Suitable aluminum catalysts for component (E) may include, for example, aluminum alcoholates such as aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butylate) , and mono (sec-butoxy) aluminum diisopropylate; or aluminum chelates such as diisopropoxyaluminum (ethylacetoacetate) , aluminum tris (ethylacetoacetate) , aluminum bis (ethyl acetoacetate) monoacetylacetonate, and aluminum tris (acetylacetonate) ; or mixtures thereof. Desirably, the condensation reaction catalyst (E) is a titanium alcoholate, a titanium chelate, or a mixture thereof.
[0056] The condensation reaction catalyst may be present in an amount of from 0.01 wt%to 5 wt%, and can be 0.01 wt%or more, 0.03 wt%or more, 0.05 wt%or more, 0.08 wt%or more, 0.09 wt%or more, even 0.10 wt%or more while at the same time is 5 wt%or less, and can be 4 wt%or less, 3 wt%or less, or even 2 wt%or less, based on the weight of component (A) .
[0057] The curable composition of the present invention may comprise or be free of component (F) an inorganic filler. Suitable fillers may comprise, for example, reinforcing fillers such as precipitated calcium carbonate, fumed silica and / or precipitated silica; non-reinforcing fillers such as crushed quartz, ground calcium carbonate, diatomaceous earths, barium sulphate, iron oxide, titanium dioxide, carbon black, talc, wollastonite, aluminite, calcium sulphate (anhydrite) , gypsum, calcium sulphate, magnesium carbonate, clays such as kaolin, aluminum trihydroxide, magnesium hydroxide (brucite) , graphite, copper carbonate, nickel carbonate, barium carbonate, and / or strontium carbonate; aluminum oxide, silicates from the group consisting of olivine group; garnet group; aluminosilicates; ring silicates; chain silicates; and sheet silicates; or mixtures thereof. Component (F) the inorganic filler may be present in an amount of from zero to 200 parts by mass, and can be greater than zero, 1 part or more, 10 parts or more, 20 parts or more, 50 parts or more, 80 parts or more, even 100 parts or more while at the same time is generally 200 parts or less, and can be 180 parts or less, 150 parts or less, even 140 parts or less, relative to 100 parts by mass of component (A) .
[0058] The curable composition of the present invention may comprise or be free of component (G) an organosiloxane having one silicon atom-bonded hydrogen atom per molecule and free of an alkenyl group and free of a silicon atom-bonded alkoxy group (also referred to as “SiH end-blocker” ) . Silicon atom-bonded groups other than silicon atom-bonded hydrogen atoms in component (G) can be the same or different and selected from a saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, such as methyl, ethyl, and propyl, or other alkyl groups; phenyl, tolyl, xylyl, benzyl, phenethyl, or other aryl groups; or combinations thereof; desirably methyl. Component (G) can be a linear structure, partially branched linear structure, branched structure, cyclic structure, network structure, and dendritic structure.
[0059] The organosiloxane for component (G) may have the structure of formula (G-I) : RG3Si-OSiHRG-OSiRG3
[0060] where each RG can be the same or different and is independently a saturated monovalent hydrocarbon group having 1 to 12 carbon atoms as described above. Desirably, each RG is methyl. The organosiloxane for component (G) may be selected from heptamethyltrisiloxane, pentamethyldisiloxane, or mixtures thereof. Component (G) the organosiloxane may be present in an amount of from zero to 5 wt%, and can be 0.05 wt%or more, 0.1 wt%or more, 0.2 wt%or more, 0.5 wt%or more, 0.8 wt%or more, even 0.9%or more while at the same time is typically 5.0 wt%or less, and can be 4.0 wt%or less, 3.0 wt%or less, 2.0 wt%or less, or even 1.0 wt%or less, based on the weight of component (A) .
[0061] The curable composition of the present invention may comprise or be free of component (H) a filler treating agent having at least one silicon atom-bonded alkoxy group. Component (H) may be selected from an alkyl trialkoxysilane, a trialkoxysilyl polydiorganosiloxane, or mixtures thereof.
[0062] The alkyl trialkoxysilane may have the chemical formula (H-I) : RFSi (ORH) 3 (H-I)
[0063] where RF is independently in each occurrence an alkyl group having 1 to 12 carbon atoms; and RH is independently in each occurrence an alkyl group having 1 to 6 carbon atoms. RH is desirably methyl so as to form methoxy groups attached to the silicon atom. A particularly desirable alkyl trialkoxysilane is methyltrimethoxysilane, n-decyltrimethoxysilane, n-octyltrimethoxysilane, or a mixture thereof.
[0064] The trialkoxysilyl polydiorganosiloxane is a polydiorganosiloxane that contains a -Si (ORE) 3 group, where RE is independently in each occurrence as described for RE herein below in (IV) . Desirably, the trialkoxysilyl polydiorganosiloxane is a mono-trialkoxysiloxy terminated polydiorganosiloxane having an average chemical structure: RC3Si [ORD2Si] hh-Y-Si (ORE) 3, where RC, RD, and RE are each independently in each occurrence an alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms such as phenyl and dimethyl phenyl, and can have 1 to 10 carbon atoms or 1 to 6 carbon atoms; subscript hh typically has a value of 20 to 130, desirably 25 to 110; and Y is O or [OSiRD2] (CH2) kk, where subscript kk has a value of 3 to 20, and can be 3 to 10, or 3 to 6. Desirably, each RC, RD, and RE is methyl. A particularly desirable monotrialkoxysiloxy-terminated polydiorganosiloxane is a monotrimethoxysiloxy and trimethylsiloxy terminated polydimethylsiloxane.
[0065] Component (H) the filler treating agent may be present in an amount of from zero to 5.0 wt%, and can be zero or more, 0.01 wt%or more, 0.05 wt%or more, 0.08 wt%or more, 0.10 wt%or more, 0.15 wt%or more, even 0.2%or more while at the same time is typically 5 wt%or less, and can be 4.0%or less, 3.0 wt%or less, 2.0 wt%or less, 1.0 wt%or less, 0.5 wt%or less, 0.2 wt%or less, 0.1 wt%or less, 0.05 wt%or less, or even 0.01 wt%or less, based on the weight of component (A) .
[0066] The curable composition of the present invention may comprise or be free of a pigment (component (I) ) . Pigments are utilized to color the composition as required. Any suitable pigment may be utilized providing it is compatible with the composition, such as carbon black, copper (II) phthalocyanine, PigmentViolet32, or mixtures thereof. The pigment may be present in an amount of from zero to 10 wt%, and can be 0.01 wt%or more, 0.05 wt%or more, 0.1 wt%or more, 0.5 wt%or more, 1 wt%or more, 1.5 wt%or more, even 2 wt%or more while at the same time is generally 10 wt%or less, and can be 8 wt%or less, 6 wt%or less, 5 wt%or less, 4 wt%or less, 3 wt%or less, 2.5 wt%or less, 1.0 wt%or less, 0.5 wt%or less, or even 0.05 wt%or less, based on the weight of component (A) .
[0067] The curable composition of the present invention may comprise or be free of a rheology modifier (component (J) ) . Rheology modifiers may include organic copolymers such as silicone polyether copolymers, silicone glycols, or mixtures thereof. The rheology modifier may be present in an amount of from zero to 5.0 wt%, and can be from 0.01 to 4 wt%, from 0.1 to 3 wt%, or from 0.5 to 2 wt%, based on the weight of component (A) .
[0068] The curable composition of the present invention may comprise or be free of other optional components including any one or any combination of more than one of the following components: heat stabilizers, thixotropic agents, fire retardants, reaction inhibitors, and antioxidants. These optional components may be present in an amount of from zero to 5 wt%, and can be from 0.01 to 4 wt%, from 0.1 to 3 wt%, or from 0.5 to 2 wt%, based on the weight of component (A) .
[0069] The present invention also relates to a process for preparing the curable composition described above, comprising admixing components (A) , (B) , (C) , (D) and (E) , and optionally other components such as components (F) , (G) , (H) , and / or (I) , described above. When the filler (F) is used, the process may include step i) mixing the filler (F) and desirably the filler treating agent (H) with component (A) first, thereby forming a mixture; and step ii) further mixing the resulting mixture with other components (i.e., the rest of components) in the curable composition. The mixture obtained in the step i) may be further heated at a temperature such that covalent linkage can be constructed between the filler and the filler treating agent, for example, at temperatures ranging from 100 to 155 ℃. Alternatively, step i) can be carried out through cold-blending process such as mixing the components at room temperature (23±2 ℃) . Desirably, mixing in step ii) is conducted at room temperature. Mixing in the process for preparing the curable composition can be conducted by conventional means at room temperature for sufficient time until homogenous. The curable composition can be a one-part composition or a multi-part composition. The curable composition is typically stored in a sealed container to prevent exposure to air and moisture. If supplied as a one-part composition, the curable composition of the present invention may be stored at room temperature for several weeks without any change in the properties of a cured product made from the curable composition, or at a temperature below 0 ℃, desirably from -30 to -20 ℃ for several months.
[0070] The curable composition described above or the curable composition prepared from the above process can be cured to form a cured product. The cured product of the curable composition is formed by curing the curable composition via hydrosilation reaction and condensation reaction simultaneously.
[0071] The present invention also includes a process for using the curable composition described above. The process comprises the steps of: a) applying the curable composition on at least one surface of a substrate; and b) curing the curable composition; thereby forming a silicone material (i.e., a cured material) . The curable composition can be applied to both surfaces of the substrate. Applying the curable composition on the substrate can be performed by any convenient means such as a gravure coater, comma coater, offset coater, offset-gravure coater, roller coater, reverse-roller coater, air-knife coater, slot die, or curtain coater. Examples of materials suitable for such substrates include unwashed aluminum diecast and organic resins such as polybutylene terephthalate (PBT) resin, polyphenylene sulfide (PPS) resin, polyimide (PI) , polyetheretherketone (PEEK) , polyethylene naphthalate (PEN) , liquid-crystal polyacrylate, polyamideimide (PAI) , polyether sulfide (PES) , polyethylene terephthalate (PET) , polycarbonate (PC) , polymethylmethacrylate (PMMA) , thermoplastic polyurethane (TPU) , thermoplastic elastomer (TPE) , polyethylene (PE) , or polypropylene (PP) .
[0072] The curable composition of the present invention is useful as a protective agent for electric or electronic components of electric or electronic devices. The present invention also relates to an electric or electronic device. The electric or electronic device comprises an electric or electronic component and a silicone material such as an encapsulant and a sealant on at least one surface of the electric or electronic component, wherein the silicone material is a cured product of the curable composition of the present invention (i.e., the curable composition in a cured formed) . The device can be made by sealing or potting the electric or electronic component using the curable composition. Curing the curable composition of the present invention may be performed by any conventional means such as at room temperature or at elevated temperatures such as 30 to 120 ℃, 40 to 100 ℃, or 50 to 80 ℃ for a time sufficient to cure the curable composition, e.g., via hydrosilation reaction and condensation reaction simultaneously. Desirably, curing is conducted at room temperature for 12 to 24 hours or at 50 to 80 ℃ for 30 to 60 minutes. The above heating step and curing step can be performed in an oven, e.g., an air circulation oven or tunnel furnace or by passing the coated film around heated cylinders.
[0073] The electric or electronic device can be made by a method that comprises: (i) applying the curable composition on and in contact with the electric or electronic component for the device, and (ii) curing the curable composition, thereby forming a cured product of the curable composition disposed on the electric or electronic component. Applying and curing the curable composition can be conducted as described above. The electronic device is not particularly limited, so long as it is enclosed or sealed. Examples of electronic devices include electronic devices that contain electrical circuits or electrodes in which metal oxide film electrodes such as indium tin oxide (ITO) are formed, and metal electrodes of silver, copper, aluminum, gold or the like on a substrate such as glass, epoxy resin, polyimide resin, phenolic resin, ceramic. The silicone material (i.e., cured product) made from the curable silicone composition of the present invention can be used for as adhesives, encapsulants, potting materials, coating materials, or sealing material. In particular, the silicone material is useful as an encapsulant for electric circuit boards. Alternatively, the curable composition of the present invention is useful as a sealing material for a structure made of metal and / or resin such as peripheral parts of electric and electronic equipment, automotive component cases, terminal boxes, lighting parts, and modules for solar batteries when applied to a circuit board for power semiconductors such as engine controls and powertrain systems in transportation equipment, and air conditioning controls, as well as storage cases thereof.
[0074] The method of making the electric or electronic device may optionally further comprise, desirably be free of, treating the substrate (i.e., an electric or electronic component) before applying the curable composition. Treating the substrate may be performed by any convenient means, such as applying a primer, or subjecting the substrate to corona-discharge treatment, etching, or plasma treatment before applying the curable composition to the component. Desirably, the treating the substrate herein excludes a cleaning process for removing soldering flux residues on the electric or electronic component, i.e., the method is free of a step of removing soldering flux residues on the electric or electronic component prior to applying the curable composition. The curable composition of the present invention is particularly suitable for use on electric or electronic components, even on those having soldering flux residues left on. The curable composition can achieve excellent inhibition resistant during curing in contact with the soldering flux (e.g., no-clean flux) , even when contact with room temperature dried soldering flux.
[0075] EXAMPLES
[0076] Some embodiments of the invention will now be described in the following Examples, wherein all percentages (%) are by weight relative to the weight of component (A) described above, unless otherwise specified. Table 1 lists the materials for use in the curable composition of the samples described herein below. SYL-OFF is a trademark of The Dow Chemical Company.
[0077] Table 1
[0078] *Viscosities of polyorganosiloxanes were measured by ASTM D 1084 Method B (for cup / spindle) and ASTM D 4287 (for cone / plate) at 25 ℃.
[0079] Inventive Examples (IEs) 1-5 and Comparative Example (CEs) 1-6 Encapsulant Composition Samples
[0080] Formulations for the samples are in Table 3, with the amount of each component reported in grams (g) . Samples were prepared by using a SpeedMixerTM DAC 400 FVZ mixer from FlackTek Inc. (South Carolina, USA) to mix the components together. Components A, F, and H were mixed at 1,500 revolutions per minute (rpm) for 45 seconds and repeated for three times in an aluminum (Al) cup and heated at 120 ℃for 1 hour under vacuum. After cooling down to room temperature, all the other components (including component I pigment) were added and mixed using FlackTek SpeedMixer for 1.5 minutes (1000 rpm for 45 seconds and then 1500 rpm for 45 seconds) to obtain silicone encapsulant compositions ( “curable composition samples” ) .
[0081] The obtained curable composition samples were evaluated for inhibition resistance according to the following test method:
[0082] Inhibition Resistance Test
[0083] Fill in an empty aluminum (Al) cup (6 cm diameter on top, 5 cm diameter on bottom and 1.5 cm in height) with 0.2 g of KESTERTM 985M Soldering Flux. The Al cup filled with the soldering flux was left to dry at room temperature (RT) for 3 hours. Then a curable composition sample was added into the Al cup to cure in contact with the soldering flux for 30 minutes at 50 ℃. After that, the obtained cured encapsulant was peeled away from the Al cup. The condition of the Al cup's bottom surface that was touching the encapsulant was visually inspected and rated according to the ratio of the area of black liquid residue (indicating the curable composition that has not cured because of touching the soldering flux) to the area of bottom surface of the Al cup given in Table 2 below, where “+” rating is the best and “+++” is the worst. Acceptable inhibition resistance is the rating of “+” . Under some circumstances, if the entire composition for a sample is still flowable after heating for 30 minutes at 50 ℃, such sample is rated as “not cured” , indicating not enough cross-linking to form a cured material, which is unacceptable.
[0084] Table 2
[0085] Table 3 contains characterization results for IEs and CEs samples. As shown in Table 3, IEs 1-5 samples comprising a specific amount of silane modified polyether (C) all achieved excellent inhibition resistance with the rating of “+” , which is much better than CEs 1-6 samples.
[0086] In contrast, CE 1 sample that is a pure hydrosilylation curable composition failed in the inhibition resistance test. Compared to CE 1 sample, addition of trimethoxysilyl-terminated polysiloxanes, together with a condensation reaction catalyst, showed some improvement on inhibition resistance but still cannot reach the requirement of “+” rating (CEs 3 and 4) . If small molecule bis (trimethoxysilyl) hexane (even with the molar amounts of alkoxyl groups higher than silane modified polyether in IEs 1-5) was used in replacement of the silane modified polyether (C) , the inhibition resistance of the obtained CE5 sample was still poor ( “+++” rating) . CE 6 sample that contains less than 3 wt%of the silane terminated polyether (C) , relative to the weight of component (A) , provided poorer inhibition resistance ( “++” rating) . CE 2 sample comprising a silane modified acrylic polymer was still flowable after heating for 30 minutes at 50 ℃, indicating the sample did not cure at all.
[0087] Table 3 Compositions and Characterization Results
[0088] Wt%of Component (C) refers to weight percentages of component (C) relative to the weight of component (A) .
[0089] Inhibition Resistance Rating was determined according to the Inhibition Resistance Test described above.
Claims
1.A curable silicone composition comprising:(A) an alkenyl-functional polyorganosiloxane having an average of at least two alkenyl groups per molecule and free of a silicon atom-bonded alkoxy group;(B) from 0.1 to 20 weight percent, based on the weight of the alkenyl-functional polyorganosiloxane (A) , of a silyl-hydride functional polyorganosiloxane having an average of at least two silicon atom-bonded hydrogen atoms per molecule and free of an alkenyl group;(C) from 3 to 50 weight percent, based on the weight of the alkenyl-functional polyorganosiloxane (A) , of a silane terminated polyether having at least two (R) m (Y) 3-m-Si groups per molecule, where each R is independently selected from a hydroxyl group and a hydrolysable group, each Y is independently an alkyl group having from 1 to 8 carbons, and subscript m is 1, 2, or 3;(D) a hydrosilation reaction catalyst present in an amount sufficient to provide 1 to 1000 ppm of platinum group metal; and(E) a condensation reaction catalyst.2.The curable silicone composition of claim 1, wherein the silane terminated polyether (C) has a backbone comprising recurring oxyalkylene units of an average formula (-CnH2n-O-) y, where subscript n is an integer of from 2 to 4 and subscript y is an integer of from 4 to 1000.3.The curable silicone composition of claim 1 or 2, wherein each (R) m (Y) 3-m-Si group is independently selected from the group consisting of - (Y) SiOH2, - (Y) 2SiOH, -YSi (ORB) 2, -Si (ORB) 3, and - (Y) 2SiORB, where each RB is independently an alkyl group having from 1 to 8 carbons.4.The curable silicone composition of any one of claims 1-3, wherein the silane terminated polyether (C) has a viscosity ranging from 100 to 1000000 centipoises as determined according to ASTM D 4287 at 25 ℃.5.The curable silicone composition of any one of claims 1-4, wherein the alkenyl-functional polyorganosiloxane (A) has an average chemical structure: RM(3-c) R’cSiO- (R’RMSiO) a- (RM2SiO) b-SiR’dRM(3-d) (A-I)where each RM is independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, each R’ is independently an alkenyl group having 2 to 12 carbon atoms, subscript a ≥ 0, subscript b > 0, subscript c is 0 or 1, subscript d is 0 or 1, (a+b) is 20 to 2000, and (a+c+d) ≥ 2.6.The curable silicone composition of any one of claims 1-5, wherein the condensation reaction catalyst (E) is selected from the group consisting of a titanium alcoholate, a titanium chelate, and mixtures thereof.7.The curable silicone composition of any one of claims 1-6, wherein the silyl-hydride functional polyorganosiloxane (B) comprises unit formula (B-I) : (RM3SiO1 / 2) p (RM2SiO2 / 2) q (RMSiO3 / 2) r (SiO4 / 2) s (RMHSiO2 / 2) t (RM2HSiO1 / 2) u (B-I) ,where each RM is independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, subscripts p, q, r, s, t, and u have values such that p≥0, q≥0, r≥0, s≥0, t≥0, u≥0, (t+u) ≥2, (p+u) ≥2, and a quantity (p+q+r+s+t+u) is sufficient to provide the silyl-hydride functional polyorganosiloxane with a degree of polymerization of 5 to 500.8.The curable silicone composition of any one of claims 1-7, wherein the molar ratio of the silicon-bonded hydrogen atoms in component (B) the silyl-hydride functional polyorganosiloxane to alkenyl groups in component (A) the alkenyl-functional polyorganosiloxane is in a range of 0.2 to 0.9.9.An electric or electronic device comprising an electric or electronic component and a silicone material on at least one surface of the electric or electronic component, wherein the silicone material is a cured product of the curable silicone composition of any one of claims 1-8.10.A method of making an electric or electronic device, comprising:i) applying the curable silicone composition of any one of claims 1-8 on and in contact with at least one surface of an electric or electronic component of the electric or electronic device, andii) curing the curable silicone composition, thereby forming a silicone material.
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