WO2016054781A1 - An organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same - Google Patents

An organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same Download PDF

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WO2016054781A1
WO2016054781A1 PCT/CN2014/088194 CN2014088194W WO2016054781A1 WO 2016054781 A1 WO2016054781 A1 WO 2016054781A1 CN 2014088194 W CN2014088194 W CN 2014088194W WO 2016054781 A1 WO2016054781 A1 WO 2016054781A1
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group
carbon atoms
organopolysiloxane
reactant
organopolysiloxane prepolymer
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PCT/CN2014/088194
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French (fr)
Inventor
Mieko SANO
Aya HIKITA
Tadashi Takano
Hao Wu
Wentao Xing
Wenjuan Tan
Juan Du
Yong Zhang
Lirong Bao
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Henkel (China) Company Limited
Henkel Japan Ltd.
Henkel Corporation
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Priority to PCT/CN2014/088194 priority Critical patent/WO2016054781A1/en
Priority to TW104132082A priority patent/TW201619243A/en
Publication of WO2016054781A1 publication Critical patent/WO2016054781A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to an organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same, particularly used as an encapsulant in light emitting diodes (LEDs) .
  • LEDs light emitting diodes
  • An encapsulant is usually used in light emitting materials, for example light emitting diodes (LEDs) for encasing the light emitting elements, for example a diode which connects with chips.
  • LEDs light emitting diodes
  • a rapid rise in temperature occurs, subjecting the encapsulant to thermal shock. Accordingly, when the LED is turned on and off repeatedly, the encapsulant is exposed to temperature cycles.
  • LEDs are also exposed to environmental changes in temperature and humidity, as well as subject to physical shocks. Therefore, optimal performance of the encapsulant used in LEDs is required.
  • organopolysiloxane compositions using silicone resins and copolymers exhibit superior heat resistance, moisture resistance and retention of transparency, in recent years, LEDs that use organopolysiloxane compositions as the essential component of encapsulants have become more prevalent.
  • JP 4766222 B discloses organopolysiloxane compositions of addition reaction type comprising an organopolysiloxane having a vinyl group, an organohydrogenpolysiloxane, a hydrosilylating catalyst, and an organosilicon compound having a silicon atom-bonded alkoxy group.
  • organopolysiloxane compositions have high moisture permeability so that the diode in a LED corrodes easily, and light reflection is decreased.
  • JP 4880907 B discloses organopolysiloxane compounds comprising an organic compound having at least two carbon-carbon double bonds which are reactive with SiH groups in a molecule, a silicon compound having at least two SiH groups in a molecule, a hydrosilylating catalyst and a thermoplastic resin as essential ingredients.
  • the thermoplastic resin used in the compound for eliminating the residual stress has poor heat resistance.
  • the cured composition produced therefrom retains surface tack so that dusts readily deposit on the surface, and thus interfere with the light transmission of LEDs.
  • JP 4267404 B discloses organopolysiloxanes comprising an organopolysiloxane having at least one alkenyl group and phenyl siloxane units, an isocyanurate compound having an alkenyl group, an organohydrogen siloxane having at least four SiH bonds in a molecule, an organosiloxane having a phenyl group and comprising two or three SiH bonds, and a hydrosilylating catalyst.
  • organopolysiloxanes create residual stresses in the LEDs and do not have sufficient mechanical strength.
  • One aspect of the present invention is an organopolysiloxane prepolymer, being a reaction product of reactants comprising:
  • R 1 to R 6 is an alkenyl group having from 2 to 20 carbon atoms, the others of R 1 to R 6 independently from each other represent optionally substituted monovalent organic group of 1 to 20 carbon atoms, selected from the group consisting of an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms,
  • the ratio of a/ (a+b+c+d) is from 0.1 to 0.8
  • the ratio of b/ (a+b+c+d) is from 0 to 0.5
  • the ratio of c/ (a+b+c+d) is from 0.2 to 0.9
  • the ratio of d/ (a+b+c+d) is from 0 to 0.2
  • the sum of a+b+c+d 1.0
  • R 7 , R 8 and R 9 independently from each other represent an alkyl group having from 1 to 12 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a monovalent organic group represented by - (CH 2 ) m -X or -(CH 2 ) p -O- (CH 2 ) q -Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 12 carbon atoms, an epoxy group having from 2 to 12 carbon atoms, and an alkoxysilyl group having from 1 to 12 carbon atoms, and at least two of R 7 , R 8 and R 9 contain an carbon-carbon double bond, and
  • a polyorganohydrogensiloxane compound comprising at least one, preferably at least two hydrogen atoms each directly bonded to a silicon atom, and
  • a further aspect of the invention is an organopolysiloxane prepolymer composition, comprising the organopolysiloxane prepolymer according to the invention.
  • Another aspect is a curable organopolysiloxane composition, comprising:
  • Yet another aspect is a cured product of the curable organopolysiloxane composition of the present invention, which can be used as an encapsulant for light emitting materials.
  • organopolysiloxane prepolymer of the present invention the organopolysiloxane prepolymer composition or the curable organopolysiloxane composition of the present invention or the cured product of the present invention in the manufacturing of optical devices.
  • the present disclosure is generally directed to an organopolysiloxane prepolymer, being a reaction product of reactants comprising:
  • R 1 to R 6 is an alkenyl group having from 2 to 20 carbon atoms, the others of R 1 to R 6 independently from each other represent optionally substituted monovalent organic group of 1 to 20 carbon atoms, selected from the group consisting of an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms,
  • the ratio of a/ (a+b+c+d) is from 0.1 to 0.8
  • the ratio of b/ (a+b+c+d) is from 0 to 0.5
  • the ratio of c/ (a+b+c+d) is from 0.2 to 0.9
  • the ratio of d/ (a+b+c+d) is from 0 to 0.2
  • the sum of a+b+c+d 1.0
  • R 7 , R 8 and R 9 independently from each other represent an alkyl group having from 1 to 12 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a monovalent organic group represented by - (CH 2 ) m -X or -(CH 2 ) p -O- (CH 2 ) q -Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 12 carbon atoms, an epoxy group having from 2 to 12 carbon atoms, and an alkoxysilyl group having from 1 to 12 carbon atoms, and at least two of R 7 , R 8 and R 9 contain an carbon-carbon double bond,
  • a polyorganohydrogensiloxane compound comprising at least one, preferably at least two hydrogen atoms each directly bonded to a silicon atom, and
  • an alkyl group having from 1 to 20 carbon atoms refers to a linear or branched moiety containing only single bonds between carbon atoms in the moiety and including, for example, C 1 -C 18 -, C 1 -C 12 -, C 1 -C 10 -, C 1 -C 8 -, C 1 -C 6 -or C 1 -C 4 -alkyl.
  • Examples thereof are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl and eicosyl.
  • an alkenyl group having from 2 to 20 carbon atoms refers to a straight or branched chain hydrocarbon having from two to twenty carbon atoms, with at least one unsaturation, and including, for example, C 2 -C 18 -, C 2 -C 12 -, C 2 -C 10 -, C 2 -C 8 -, C 2 -C 6 -or C 2 -C 4 -alkenyl.
  • Typical alkenyl groups having from 2 to 20 carbon atoms are groups such as vinyl, allyl, 1-propen-2-yl, 1-buten-4-yl, 2-buten-4-yl and 1-penten-5-yl.
  • an alkoxy group having from 1 to 20 carbon atoms refers to the group -O-R where R is an alkyl having from 1 to 20 carbon atoms as defined above.
  • an aromatic group having from 6 to 20 carbon atoms refers to an unsaturated aromatic carbocyclic group of from 6 to 20 carbon atoms having a single ring (e.g. , phenyl) or multiple condensed (fused) rings, wherein at least one ring is aromatic (e.g. , naphthyl, dihydrophenanthrenyl, fluorenyl, or anthryl) .
  • Preferred aromatic groups include phenyl, naphthyl and the like.
  • the above groups may be further substituted or unsubstituted.
  • substituent group (s) that is (are) one or more group (s) independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl) alkyl, hydroxy, protected hydroxyl, alkoxy, aryloxy, acyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfona
  • substituents on an aryl group may form a non-aromatic ring fused to the aryl group, including a cycloalkyl, cycloalkenyl, cycloalkynyl, and heterocyclyl.
  • reactant (a) can be identified with reference to certain units contained in a siloxane structure. These units have been designated as M, D, T and Q units, which represent, respectively, units with the empirical formulae R 1 R 2 R 3 SiO 1/2 , R 4 R 5 SiO 2/2 , R 6 SiO 3/2 and SiO 4/2 , wherein each of R 1 to R 6 represents a monovalent substituent as defined above.
  • M, D, T and Q refer respectively, to the fact that the unit is monofunctional, difunctional, trifunctional or tetrafunctional.
  • the units of M, D, T and Q are arranged randomly or in blocks. For example, blocks of units of M, D, T and Q may follow one another, but the individual units may also be linked in random distribution, depending upon the siloxane used during preparation.
  • At least one of R 1 to R 6 in the reactant (a) is an alkenyl group having from 2 to 20, preferably from 2 to 8 carbon atoms, and the others of R 1 to R 6 are independently from each other selected from an alkyl group having from 1 to 20, preferably from 1 to 8 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 8 carbon atoms, and an aromatic group having from 6 to 20, preferably 6 to 14 carbon atoms.
  • the alkenyl group for R 1 to R 6 is selected from the group consisting of vinyl, allyl, methallyl, 1, 1-dimethylallyl, 1-butenyl, 2-butenyl, 1, 3-pentadienyl, 1-hexenyl and 1-octenyl;
  • the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, and octyl.
  • the alkoxyl group for R 1 to R 6 is preferably selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy.
  • the aromatic group for R 1 to R 6 is preferably selected from the group consisting of phenyl, biphenyl, 1, 2, 3, 4-tetrahydronaphthyl, naphthyl, anthryl, phenanthryl, 9-fluorenyl, and dibenzocycloheptatrienyl.
  • from 15 to 65 mol%, preferably from 20 to 50 mol%of R 1 to R 6 is an aromatic group having from 6 to 20 carbon atoms, preferably aromatic group having from 6 to 14 carbon atoms, more preferably phenyl.
  • From 1 to 50 mol%, preferably from 5 to 30 mol%of R 1 to R 6 in one molecule of the reactant (a) are alkenyl groups having from 2 to 20 carbon atoms, preferably an alkenyl group having from 2 to 8 carbon atoms, more preferably vinyl or allyl.
  • the ratio of a/ (a+b+c+d) is from 0.1 to 0.8, more preferably from 0.2 to 0.6
  • the ratio of b/ (a+b+c+d) is from 0 to 0.5, more preferably from 0 to 0.3
  • the ratio of c/(a+b+c+d) is from 0.2 to 0.9, more preferably from 0.3 to 0.7
  • the ratio of d/(a+b+c+d) is from 0 to 0.2, more preferably from 0 to 0.1
  • the sum of a+b+c+d is 1.0.
  • the reactant (a) may be produced by the condensation reaction of at least one aromatic alkoxysilane and at least one alkenyl alkoxysilane.
  • the aromatic group in the aromatic alkoxysilane may have from 6 to 20 carbon atoms, preferably from 6 to 12 carbon atoms.
  • the alkenyl group in the alkenyl alkoxysilane may have from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms.
  • the alkoxy group in the aromatic alkoxysilane and alkenyl alkoxysilane may have from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms.
  • the aromatic alkoxysilane may be exemplified by phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, phenyldimethoxymethylsilane, phenylmethoxydimethylsilane, diphenylmethoxymethylsilane, phenyldimethoxyethylsilane, phenylmethoxydiethylsilane, and diphenylmethoxyethylsilane.
  • the alkenyl alkoxysilane may be exemplified by vinyltrimethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, vinyltriethoxysilane, divinyldiethoxysilane, trivinylethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, divinylmethoxymethylsilane, vinyldimethoxyethylsilane, vinylmethoxydiethylsilane, divinylmethoxyethylsilane, vinyldiethoxymethylsilane, vinylethoxydimethylsilane, divinylethoxymethylsilane, vinyldiethoxyethylsilane, vinylethoxydiethylsilane, divinylethoxydiethylsilane, allyltrimethoxysilane, diallyldimethoxysilane, triallylmethoxysilane, allyltrie
  • aromatic alkoxysilane and alkenyl alkoxysilane having higher alkoxy for example, propoxy, butoxy, hexoxy, and octoxy also can be used in the present invention.
  • the reactant (a) of the organopolysiloxane prepolymer according to the present invention is a vinyl phenyl silicone resin produced by the reaction between phenyltrimethoxysilane and vinyldimethylethoxysilane in acidic condition.
  • the reactant (a) is preferably present in an amount of from 5%to 80%, more preferably 25%to 70%by weight of all reactants for the organopolysiloxane prepolymer.
  • reactant (b) is a cyclic isocyanurate having two or more ethylenically unsaturated double bonds which is represented by formula (2) .
  • R 7 , R 8 and R 9 independently from each other represent an alkyl group having from 1 to 12, preferably 1 to 6 carbon atoms, an aromatic group having from 6 to 20, preferably 6 to 12 carbon atoms, a monovalent organic group represented by - (CH 2 ) m -X or - (CH 2 ) p -O- (CH 2 ) q -Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 12, preferably 2 to 8 carbon atoms, an epoxy group having from 2 to 12, preferably 2 to 8 carbon atoms, and an alkoxysilyl group having from 1 to 12, preferably 1 to 8 carbon atoms.
  • the alkyl group for R 7 , R 8 and R 9 is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, and octyl;
  • the alkenyl group is preferably selected from the group consisting of vinyl, allyl, methallyl, 1, 1-dimethylallyl, 1-butenyl, 2-butenyl, 1, 3-pentadienyl, 1-hexenyl and 1-octenyl.
  • the epoxy group for R 7 , R 8 and R 9 is preferably selected from the group consisting of glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, 3, 4-epoxycyclohexylethyl, 3, 4-epoxycyclohexyl-propyl, 3, 4-epoxynorbornenylethyl, 2- (3, 4-epoxy-3-methylcyclohexyl) -2-methylethyl.
  • the alkoxysilyl group for R 7 , R 8 and R 9 is preferably selected from the group consisting of trimethoxysilyl, triethoxysilyl, tripropoxysilyl, triisopropoxysilyl, tricyclopropyloxysilyl, tricyclohexyloxysilyl, dimethoxyethoxysilyl, and methoxydiethoxysilyl.
  • the reactant (b) is preferably present in an amount of from 1%to 45%, particularly preferred 5%to 35%by weight of all reactants for the organopolysiloxane prepolymer.
  • the reactant (c) is preferably represented by the average structural formula (3)
  • R 7 is an optionally substituted monovalent organic group which is selected from, as defined above, an alkyl group having from 1 to 20 carbon atoms, an aryl group or arylene group having from 6 to 20 carbon atoms, and the combination thereof; e is a positive number of from 0.7 to 2.1, preferably from 0.9 to 2.1; f is a positive number of from 0.001 to 1.0, preferably from 0.01 to 1.0; and the sum of e+f is from 0.8 to 3, preferably from 1 to 2.5.
  • the reactant (c) may be exemplified by 1, 3-dimethyl-1, 3-diphenyl-disiloxane, 3-(dimethylvinylsiloxy) -1, 1, 5, 5-tetramethyl-3-phenyltrisiloxane, 3-(dimethylvinylsiloxy) -1, 1, 5, 5-tetramethyl-3-methyltrisiloxane, 1, 1, 3, 3-tetramethyl-disiloxane, 1, 1, 5, 5-tetramethyl-3, 3-diphenyltrisiloxane, 1, 1, 7, 7-tetramethyl-3, 5-diphenyltetrasiloxane, 1, 9, 9-tetramethyl-3, 5, 7-triphenylpentasiloxane, 1, 1, 11, 11-tetramethyl-3, 5, 7, 9-tetraphenylhexasiloxane, 1, 1, 3, 3, 5, 5, 7, 7-octamethyltetrasiloxane, 1, 1, 3, 3-tetramethyldisi
  • 1, 1, 5, 5-tetramethyl-3, 3-diphenyltrisiloxane is used as the reactant (c) for the preparation of the organopolysiloxane prepolymer.
  • the reactant (c) is preferably present in an amount of from 1%to 50%, more preferably 5%to 40%by weight of all reactants for the organopolysiloxane prepolymer.
  • hydrosilylation catalyst (I) it is possible to use all catalysts which are useful for the addition of Si-bonded hydrogen onto aliphatically unsaturated compounds.
  • catalysts are compounds or complexes of precious metals comprising platinum, ruthenium, iridium, rhodium and palladium, such as, for example, platinum halides, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H 2 PtCl 6 .6H 2 O and cyclohexanone, platinum-vinylsiloxane complexes, in particular platinum-divinyltetramethyldisiloxane complexes with or without a content of detectable inorganically bonded halogen, bis ( ⁇ -picolin)
  • complexes of iridium with cyclooctadienes such as, for example, ⁇ -dichlorobis (cyclooctadiene) -diiridium (I) , can also be used in the present invention.
  • the catalyst is a compound or complex of platinum, preferably selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum and 2 ,4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetramethyldisiloxane complex, and the combination thereof, and most preferably platinum-divinyltetramethyldisiloxane complexes.
  • platinum preferably selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum and 2 ,4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetra
  • the hydrosilylation catalyst (I) is used for preparing the organopolysiloxane prepolymer according to the present invention preferably in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, based on the total weight of all reactants.
  • the present invention provides an organopolysiloxane prepolymer, which is a reaction product of reactants comprising:
  • the present invention provides organopolysiloxane prepolymer compositions, comprising the organopolysiloxane prepolymer according to the present invention.
  • the organopolysiloxane prepolymer (composition) may also optionally comprise additional components/reactants.
  • additional components/reactants include, but are not limited to a curing retarder, a viscosity regulating agent and an adhesion promoter.
  • the curing retarder may be added to the reactants to control the reaction, and may be selected from the group consisting of aliphatic unsaturated compounds, organic phosphorous compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the combination thereof, and more preferably is selected from 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane, 3-methyl butynol, 1-ethynylcyclohexanol, benzotiazol, tert-butyl hydroperoxide.
  • the curing retarders which can be used for the organopolysiloxane prepolymer are preferably present in an amount of from 0.1 to 1000 mols, more preferably from 1 to 50 mols per mol of the hydrosilylation catalyst (I) .
  • the viscosity regulating agent may be added when preparing the organopolysiloxane prepolymer.
  • Non-limiting examples are linear, cyclic, network-type organopolysiloxanes, and organic solvents well known to a person skilled in the art.
  • the specific selection of the viscosity regulating agent will depend on the practical need, and will be easily determined by a skilled artisan.
  • the adhesion promoter may be added when preparing the organopolysiloxane prepolymer.
  • Non-limiting examples are silane coupling agents, organosilicon compounds containing SiH groups, alkenyl groups, alkoxysilyl groups and epoxy groups, isocyanurate compounds, and combination thereof, and more preferably selected from vinyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, tris- (trimethoxysilylpropyl) isocyanurate, monoallyldiglycidylisocyanurate, and combination thereof.
  • the adhesion promoter which can be used for the organopolysiloxane prepolymer is preferably present in an amount of from less than 10%, more preferably less than
  • Another aspect is directed to a curable organopolysiloxane composition, comprising:
  • the component (b) is preferably represented by the average compositional formula (4) :
  • R 7 is a monovalent organic group, independently selected from an alkyl group having from 1 to 20 carbon atoms, an aryl group or arylene groups having from 6 to 20 carbon atoms, and the combination thereof; g is a positive number of from 0.7 to 2.1, preferably from 0.9 to 2.1, h is a positive number of from 0.001 to 1.0, preferably from 0.01 to 1.0, and the sum of g+h is from 0.8 to 3, preferably from 1 to 2.5, wherein at least one of R 7 is aryl or arylene.
  • the component (b) is selected from the group consisting of hydride terminated methylhydrosiloxane-phenylmethylsiloxane copolymers, hydride terminated polydimethylphenylsiloxanes, hydride terminated polyphenyl (dimethylsiloxy) siloxanes, hydride terminated polydiphenylsiloxanes, hydride terminated methyl hydrosiloxane-phenylmethylsiloxane copolymers, and combination thereof.
  • the component (b) is a hydride terminated polyphenyl (dimethylsiloxy) siloxane commercially available under the trade name of KM-390 or a hydride terminated polydiphenylsiloxane available under the trade name of KM-391 from Wuhan Kemi-Works Chemical.
  • the amount of the component (b) of the organopolysiloxane prepolymer is from 1 to 40%, preferably from 5 to 30%by weight of the total amount of components (a) and (b) of the curable organopolysiloxane composition.
  • the component (b) of the organopolysiloxane prepolymer is present in an amount so as to provide from 0.1 to 5, preferably 1.0 to 3.0 moles of SiH bonds per one mole of the alkenyl group comprised in components (a) .
  • the curable organopolysiloxane composition also contains a hydrosilylation catalyst used for hydrosilylation.
  • a hydrosilylation catalyst used for hydrosilylation As hydrosilylation catalyst (II) , it is possible to use all catalysts which are useful for the addition of Si-bonded hydrogen onto aliphatically unsaturated compounds.
  • the hydrosilylation catalysts (I) and (II) used in the present invention may be the same or different, either singly or in combination. Examples of such catalysts are the same as defined above for the hydrosilylation catalysts (I) .
  • the hydrosilylation catalyst (II) is used for preparing the curable organopolysiloxane composition according to the present invention preferably in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, based on the total weight of all components.
  • the curable organopolysiloxane composition may also optionally comprise additional components.
  • additional components include, but are not limited to a curing retarder, a viscosity regulating agent, an adhesion promoter, an antioxidant/thermostabilizer, a light stabilizer, a filler, a plasticizer, a dye, a pigment, and combination thereof.
  • the curing retarder, viscosity regulating agent, adhesion promoter optionally used in the curable organopolysiloxane composition are given as defined above.
  • the antioxidant or thermostabilizer useful in the curable organopolysiloxane composition includes but is not limited to hindered phenols, phosphites, thioethers, and the examples are tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (2, 4-di-tert-butylphenyl) phosphite, 2, 2'-Methylenebis (4, 6-di-tert-butyl-phenyl) -2-ethylhexyl phosphite, 2, 2-Bis [ [3- (dodecylthio) -1-oxopropoxy] methyl] propane-1, 3-diyl, bis [3
  • the antioxidant is used in the curable organopolysiloxane composition preferably in an amount of 10 to 10,000 ppm, more preferably from 100 to 1,000 ppm, based on the total amount of all components of the curable organopolysiloxane composition.
  • the light stabilizer useful in the curable organopolysiloxane composition includes but is not limited to hindered amine light stabilizers and ultraviolet absorbents, and the examples are 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2, 2’ -dihydroxy-4, 4’ -dimethoxybenzophenone, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) butane-1, 2, 3, 4-tetracarboxylate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, and combination thereof.
  • hindered amine light stabilizers and ultraviolet absorbents examples are 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2, 2’ -dihydroxy-4, 4’ -dimethoxybenzophenone, tetrakis (2, 2, 6, 6-tetramethyl-4-
  • the light stabilizer is preferably used in the curable organopolysiloxane composition in an amount of 10 to 10,000 ppm, more preferably from 100 to 1,000 ppm, based on the total amount of all components of the curable organopolysiloxane composition.
  • Fillers may also be comprised in the curable organopolysiloxane composition, and may be selected from the group consisting of finely divided silica, calcium carbonate, quartz powder, aluminium hydroxide, zirconium silicate, diatomaceous earth, titanium dioxide, and combination thereof.
  • the present invention also provides a cured product obtained from the curable organopolysiloxane composition as described above.
  • the organopolysiloxane prepolymer, the organopolysiloxane prepolymer composition or the curable organopolysiloxane composition or the cured product can be used in the manufacturing of optical devices, especially light emitting materials, e. g. LEDs applied for instance in general lighting equipment, backlight of mobile phone, tablets, PC, or TV, and light source for automotive. Others uses includes coating, die attach and reflector for LED.
  • light emitting materials e. g. LEDs applied for instance in general lighting equipment, backlight of mobile phone, tablets, PC, or TV, and light source for automotive. Others uses includes coating, die attach and reflector for LED.
  • the cured products When used as an encapsulant for LEDs, the cured products provide excellent properties in thermal resistance, optical coloration and moisture permeability at the same time. Besides, the cured products exhibit high adhesiveness and toughness.
  • the vinyl phenyl silicone resin was prepared according to conventional industrial method as below: 63.72 Kg phenyltrimethoxysilane, 10.38 Kg vinyldimethylethoxysilane, 31.50 Kg toluene and 14.04 Kg 0.1M HCl aqueous were pumped into a 50 L glass reactor in this order under stirring. The mixture was placed on an oil bath heat up to 65°C and kept for 4 hours, and then the volatile compounds was vacuumed to obtain a vinyl phenyl silicone resin as a colorless clear liquid. The vinyl content of the product is 2.1 mmol/g.
  • Examples 1 to 3 and Comparative Examples 1 and 2 were tested for their performance in luminous maintenance after Sulfur test and the TCT failure test.
  • Each of the curable compositions from Examples 1 to 3 and Comparative Examples 1 and 2 were dispensed in a LED device (5050 size, 1W power consumption) and cured at 80°C for 1h and at 150°C for 5h in an oven to prepare a resin sample.
  • the resin sample was put in a container of 3.3L that spreads sulfur powder of 22g all over the bottom surface. The container was kept at 70°C for 96 hours.
  • Luminous flux was measured by integrating sphere (Otsuka Denshi, HM-9050B) and the measurement was conducted before testing and after 96 hours exposure in sulfur. The measured luminous flux values prior to test and after 96 hours were compared to find the degradation degree.
  • the luminous maintenance (%) after sulfur test was calculated as dividing the luminous flux values prior to test by the luminous flux values after 96 hours.
  • the luminous flux value is typically influenced by the factors including optical coloration, moisture permeability, adhesion and toughness of the cured product.
  • Each of the curable compositions from Examples 1 to 3 and Comparative Examples 1 and 2 were dispensed in a LED device (3528 size, 0.15W power consumption) and cured at 80°C for 1h and at 150°C for 5h in an oven to prepare a resin sample.
  • the sample was subjected to a thermal cycle of -40°C for 30min and 100°C for 30min.
  • the cracking or delamination of the sample was visually observed by microscope after 500 cycles.
  • the failure ratio (%) was calculated as dividing the number of cracked or delaminated samples by the total number of samples.
  • the failure ratio (%) after TCT is typically influenced by the thermal resistance of the curable product.
  • Table 1 Test results of luminous maintenance after Sulfur test and failure ratio after TCT test
  • each of the Examples 1 to 3 exhibited excellent performance in both of luminous maintenance after Sulfur test and failure ratio after TCT test.
  • Comparative Example 1 Although Comparative Example 1 also possessed a failure ratio after TCT test as good as Example 1, the luminous maintenance after Sulfur test of Comparative Example 1 was significantly deteriorated to 60%, which cannot not be accepted in the art. It is believed that the presence of cyclic isocyanurates which provides a triazine structure in the prepolymer product enhanced the stability and reliability of the final cured product in all of optical coloration, moisture permeability and thermal resistance.
  • Comparative Example 2 possessed a luminous maintenance as good as Examples 1-3, the failure ratio after TCT test of Comparative Example 2 was significantly deteriorated to 80%, which cannot be accepted in the art. It is believed that the two preparation steps of prepolymer and curable composition is significantly important to increase the thermal resistance of the cured product.

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Abstract

The present invention discloses an organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same, particularly used as an encapsulant in light emitting diodes.

Description

An organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same Technical Field
The present invention relates to an organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same, particularly used as an encapsulant in light emitting diodes (LEDs) .
Background
An encapsulant is usually used in light emitting materials, for example light emitting diodes (LEDs) for encasing the light emitting elements, for example a diode which connects with chips. During the operation of LEDs, a rapid rise in temperature occurs, subjecting the encapsulant to thermal shock. Accordingly, when the LED is turned on and off repeatedly, the encapsulant is exposed to temperature cycles. In addition to normal use, LEDs are also exposed to environmental changes in temperature and humidity, as well as subject to physical shocks. Therefore, optimal performance of the encapsulant used in LEDs is required.
Since organopolysiloxane compositions using silicone resins and copolymers exhibit superior heat resistance, moisture resistance and retention of transparency, in recent years, LEDs that use organopolysiloxane compositions as the essential component of encapsulants have become more prevalent.
JP 4766222 B discloses organopolysiloxane compositions of addition reaction type comprising an organopolysiloxane having a vinyl group, an organohydrogenpolysiloxane, a hydrosilylating catalyst, and an organosilicon compound having a silicon atom-bonded alkoxy group. Such organopolysiloxane compositions have high moisture permeability so that the diode in a LED corrodes easily, and light reflection is decreased.
JP 4880907 B discloses organopolysiloxane compounds comprising an organic compound having at least two carbon-carbon double bonds which are reactive with SiH groups in a molecule, a silicon compound having at least two SiH groups in a molecule, a hydrosilylating catalyst and a thermoplastic resin as essential  ingredients. The thermoplastic resin used in the compound for eliminating the residual stress has poor heat resistance. In addition, when an attempt is made to improve the crack resistance by adjusting the composition of the compound, the cured composition produced therefrom retains surface tack so that dusts readily deposit on the surface, and thus interfere with the light transmission of LEDs.
JP 4267404 B discloses organopolysiloxanes comprising an organopolysiloxane having at least one alkenyl group and phenyl siloxane units, an isocyanurate compound having an alkenyl group, an organohydrogen siloxane having at least four SiH bonds in a molecule, an organosiloxane having a phenyl group and comprising two or three SiH bonds, and a hydrosilylating catalyst. Such organopolysiloxanes create residual stresses in the LEDs and do not have sufficient mechanical strength.
Therefore, it is the object of the present invention to develop an organopolysiloxane composition especially useful as the encapsulant for LEDs, which can overcome at least one of these challenges and has a long-term reliability during the use of the LEDs. These problems are solved by the following subject matter in the present invention.
Summary of the Invention
One aspect of the present invention is an organopolysiloxane prepolymer, being a reaction product of reactants comprising:
(a) an organopolysiloxane compound having at least two ethylenically unsaturated double bonds represented by the average compositional formula (1) :
(R1R2R3SiO1/2) a (R4R5SiO2/2) b (R6SiO3/2) c (SiO4/2) d                  (1) ,
wherein
at least one of R1 to R6 is an alkenyl group having from 2 to 20 carbon atoms, the others of R1 to R6 independently from each other represent optionally substituted monovalent organic group of 1 to 20 carbon atoms, selected from the group consisting of an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms,
from 15 to 65 mol％of R1 to R6 in one molecule of the organopolysiloxane  compound are an aromatic group having from 6 to 20 carbon atoms, from 1 to 50 mol％of R1 to R6 in one molecule of the organopolysiloxane compound are an alkenyl group having from 2 to 20 carbon atoms, and the total mol％of R1 to R6 in one molecule of the organopolysiloxane compound is 100 mol％,
the ratio of a/ (a+b+c+d) is from 0.1 to 0.8, the ratio of b/ (a+b+c+d) is from 0 to 0.5, the ratio of c/ (a+b+c+d) is from 0.2 to 0.9, the ratio of d/ (a+b+c+d) is from 0 to 0.2, and the sum of a+b+c+d ＝ 1.0,
(b) a cyclic isocyanurate having two or more ethylenically unsaturated double bonds which is represented by formula (2)
Figure PCTCN2014088194-appb-000001
wherein
R7, R8 and R9 independently from each other represent an alkyl group having from 1 to 12 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a monovalent organic group represented by - (CH2) m-X or -(CH2) p-O- (CH2) q-Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 12 carbon atoms, an epoxy group having from 2 to 12 carbon atoms, and an alkoxysilyl group having from 1 to 12 carbon atoms, and at least two of R7, R8 and R9 contain an carbon-carbon double bond, and
(c) a polyorganohydrogensiloxane compound comprising at least one, preferably at least two hydrogen atoms each directly bonded to a silicon atom, and
(d) an hydrosilylation catalyst (I) .
A further aspect of the invention is an organopolysiloxane prepolymer composition, comprising the organopolysiloxane prepolymer according to the invention.
Another aspect is a curable organopolysiloxane composition, comprising:
(a) the organopolysiloxane prepolymer according to the present invention,
(b) an organohydrogenpolysiloxane having at least two Si-H groups in one molecule, and
(c) a hydrosilylation catalyst (II) .
Yet another aspect is a cured product of the curable organopolysiloxane composition of the present invention, which can be used as an encapsulant for light emitting materials.
Yet another aspect is the use of the organopolysiloxane prepolymer of the present invention, the organopolysiloxane prepolymer composition or the curable organopolysiloxane composition of the present invention or the cured product of the present invention in the manufacturing of optical devices.
Other features and aspects of the subject matter are set forth in greater detail below.
Detailed Description
It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
The Organopolysiloxane Prepolymer
In one aspect, the present disclosure is generally directed to an organopolysiloxane prepolymer, being a reaction product of reactants comprising:
(a) an organopolysiloxane compound having at least two ethylenically unsaturated double bonds represented by the average compositional formula (1) :
(R1R2R3SiO1/2) a (R4R5SiO2/2) b (R6SiO3/2) c (SiO4/2) d                   (1) , 
wherein
at least one of R1 to R6 is an alkenyl group having from 2 to 20 carbon atoms, the others of R1 to R6 independently from each other represent optionally substituted monovalent organic group of 1 to 20 carbon atoms, selected from the group consisting of an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms,
from 15 to 65 mol％of R1 to R6 in one molecule of the organopolysiloxane compound are an aromatic group having from 6 to 20 carbon atoms, from 1 to  50 mol％of R1 to R6 in one molecule of the organopolysiloxane compound are an alkenyl group having from 2 to 20 carbon atoms, and the total mol％of R1 to R6 in one molecule of the organopolysiloxane compound is 100 mol％,
the ratio of a/ (a+b+c+d) is from 0.1 to 0.8, the ratio of b/ (a+b+c+d) is from 0 to 0.5, the ratio of c/ (a+b+c+d) is from 0.2 to 0.9, the ratio of d/ (a+b+c+d) is from 0 to 0.2, and the sum of a+b+c+d ＝ 1.0,
(b) a cyclic isocyanurate having two or more ethylenically unsaturated double bonds which is represented by formula (2)
Figure PCTCN2014088194-appb-000002
wherein
R7, R8 and R9 independently from each other represent an alkyl group having from 1 to 12 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a monovalent organic group represented by - (CH2) m-X or -(CH2) p-O- (CH2) q-Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 12 carbon atoms, an epoxy group having from 2 to 12 carbon atoms, and an alkoxysilyl group having from 1 to 12 carbon atoms, and at least two of R7, R8 and R9 contain an carbon-carbon double bond,
(c) a polyorganohydrogensiloxane compound comprising at least one, preferably at least two hydrogen atoms each directly bonded to a silicon atom, and
(d) an hydrosilylation catalyst (I) .
As used herein, “an alkyl group having from 1 to 20 carbon atoms” refers to a linear or branched moiety containing only single bonds between carbon atoms in the moiety and including, for example, C1-C18-, C1-C12-, C1-C10-, C1-C8-, C1-C6-or C1-C4-alkyl. Examples thereof are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl and eicosyl.
As used herein, “an alkenyl group having from 2 to 20 carbon atoms” refers to a straight or branched chain hydrocarbon having from two to twenty carbon atoms, with at least one unsaturation, and including, for example, C2-C18-, C2-C12-, C2-C10-, C2-C8-, C2-C6-or C2-C4-alkenyl. Typical alkenyl groups having from 2 to 20 carbon atoms are groups such as vinyl, allyl, 1-propen-2-yl, 1-buten-4-yl, 2-buten-4-yl and 1-penten-5-yl.
As used herein, “an alkoxy group having from 1 to 20 carbon atoms” refers to the group -O-R where R is an alkyl having from 1 to 20 carbon atoms as defined above. 
As used herein, “an aromatic group having from 6 to 20 carbon atoms” refers to an unsaturated aromatic carbocyclic group of from 6 to 20 carbon atoms having a single ring (e.g. , phenyl) or multiple condensed (fused) rings, wherein at least one ring is aromatic (e.g. , naphthyl, dihydrophenanthrenyl, fluorenyl, or anthryl) . Preferred aromatic groups include phenyl, naphthyl and the like.
As used herein, the above groups may be further substituted or unsubstituted. When substituted, hydrogen atoms on the groups are replaced by substituent group (s) that is (are) one or more group (s) independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl) alkyl, hydroxy, protected hydroxyl, alkoxy, aryloxy, acyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, protected C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl, trihalomethanesulfonamido, and amino, including mono-and di-substituted amino groups, and the protected derivatives thereof. In case that an aryl is substituted, substituents on an aryl group may form a non-aromatic ring fused to the aryl group, including a cycloalkyl, cycloalkenyl, cycloalkynyl, and heterocyclyl.
Reactant (a)
As used herein, the structure of (R1R2R3SiO1/2) a (R4R5SiO2/2) b (R6SiO3/2) c (SiO4/2) d represent reactant (a) can be identified with reference to certain units contained in a  siloxane structure. These units have been designated as M, D, T and Q units, which represent, respectively, units with the empirical formulae R1R2R3SiO1/2, R4R5SiO2/2, R6SiO3/2 and SiO4/2, wherein each of R1 to R6 represents a monovalent substituent as defined above. The letter designations M, D, T and Q refer respectively, to the fact that the unit is monofunctional, difunctional, trifunctional or tetrafunctional. The units of M, D, T and Q are arranged randomly or in blocks. For example, blocks of units of M, D, T and Q may follow one another, but the individual units may also be linked in random distribution, depending upon the siloxane used during preparation.
In the organopolysiloxane prepolymer according to the present invention, at least one of R1 to R6 in the reactant (a) is an alkenyl group having from 2 to 20, preferably from 2 to 8 carbon atoms, and the others of R1 to R6 are independently from each other selected from an alkyl group having from 1 to 20, preferably from 1 to 8 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 8 carbon atoms, and an aromatic group having from 6 to 20, preferably 6 to 14 carbon atoms. 
Preferably, the alkenyl group for R1 to R6 is selected from the group consisting of vinyl, allyl, methallyl, 1, 1-dimethylallyl, 1-butenyl, 2-butenyl, 1, 3-pentadienyl, 1-hexenyl and 1-octenyl； the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, and octyl. The alkoxyl group for R1 to R6 is preferably selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy. The aromatic group for R1 to R6 is preferably selected from the group consisting of phenyl, biphenyl, 1, 2, 3, 4-tetrahydronaphthyl, naphthyl, anthryl, phenanthryl, 9-fluorenyl, and dibenzocycloheptatrienyl.
In one molecule of the reactant (a) of the organopolysiloxane prepolymer, from 15 to 65 mol％, preferably from 20 to 50 mol％of R1 to R6 is an aromatic group having from 6 to 20 carbon atoms, preferably aromatic group having from 6 to 14 carbon atoms, more preferably phenyl. From 1 to 50 mol％, preferably from 5 to 30 mol％of R1 to R6 in one molecule of the reactant (a) are alkenyl groups having from 2 to 20 carbon atoms, preferably an alkenyl group having from 2 to 8 carbon atoms, more preferably vinyl or allyl.
In the reactant (a) of the organopolysiloxane prepolymer according to the present invention, the ratio of a/ (a+b+c+d) is from 0.1 to 0.8, more preferably from 0.2 to 0.6, the ratio of b/ (a+b+c+d) is from 0 to 0.5, more preferably from 0 to 0.3, the ratio of c/(a+b+c+d) is from 0.2 to 0.9, more preferably from 0.3 to 0.7, the ratio of d/(a+b+c+d) is from 0 to 0.2, more preferably from 0 to 0.1, and the sum of a+b+c+d is 1.0.
The reactant (a) may be produced by the condensation reaction of at least one aromatic alkoxysilane and at least one alkenyl alkoxysilane.
The aromatic group in the aromatic alkoxysilane may have from 6 to 20 carbon atoms, preferably from 6 to 12 carbon atoms. The alkenyl group in the alkenyl alkoxysilane may have from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms. The alkoxy group in the aromatic alkoxysilane and alkenyl alkoxysilane may have from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms.
The aromatic alkoxysilane may be exemplified by phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, phenyldimethoxymethylsilane, phenylmethoxydimethylsilane, diphenylmethoxymethylsilane, phenyldimethoxyethylsilane, phenylmethoxydiethylsilane, and diphenylmethoxyethylsilane.
The alkenyl alkoxysilane may be exemplified by vinyltrimethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, vinyltriethoxysilane, divinyldiethoxysilane, trivinylethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, divinylmethoxymethylsilane, vinyldimethoxyethylsilane, vinylmethoxydiethylsilane, divinylmethoxyethylsilane, vinyldiethoxymethylsilane, vinylethoxydimethylsilane, divinylethoxymethylsilane, vinyldiethoxyethylsilane, vinylethoxydiethylsilane, divinylethoxydiethylsilane, allyltrimethoxysilane, diallyldimethoxysilane, triallylmethoxysilane, allyltriethoxysilane, diallyldiethoxysilane, triallylethoxysilane, allyldimethoxymethylsilane, allylmethoxydimethylsilane, diallylmethoxymethylsilane, allyldimethoxyethylsilane,  allylmethoxydiethylsilane, diallylmethoxyethylsilane, allyldiethoxymethylsilane, allylethoxydimethylsilane, diallylethoxymethylsilane, allyldiethoxyethylsilane, allylethoxydiethylsilane, and diallylethoxydiethylsilane.
In addition, other aromatic alkoxysilane and alkenyl alkoxysilane having higher alkoxy, for example, propoxy, butoxy, hexoxy, and octoxy also can be used in the present invention.
In one particular embodiment, the reactant (a) of the organopolysiloxane prepolymer according to the present invention is a vinyl phenyl silicone resin produced by the reaction between phenyltrimethoxysilane and vinyldimethylethoxysilane in acidic condition.
The reactant (a) is preferably present in an amount of from 5％to 80％, more preferably 25％to 70％by weight of all reactants for the organopolysiloxane prepolymer.
Reactant (b)
In the present invention, reactant (b) is a cyclic isocyanurate having two or more ethylenically unsaturated double bonds which is represented by formula (2) .
In the reactant (b) , R7, R8 and R9 independently from each other represent an alkyl group having from 1 to 12, preferably 1 to 6 carbon atoms, an aromatic group having from 6 to 20, preferably 6 to 12 carbon atoms, a monovalent organic group represented by - (CH2) m-X or - (CH2) p-O- (CH2) q-Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 12, preferably 2 to 8 carbon atoms, an epoxy group having from 2 to 12, preferably 2 to 8 carbon atoms, and an alkoxysilyl group having from 1 to 12, preferably 1 to 8 carbon atoms.
The alkyl group for R7, R8 and R9 is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, and octyl； the alkenyl group is preferably selected from the group consisting of vinyl, allyl, methallyl, 1, 1-dimethylallyl,  1-butenyl, 2-butenyl, 1, 3-pentadienyl, 1-hexenyl and 1-octenyl. The epoxy group for R7, R8 and R9 is preferably selected from the group consisting of glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, 3, 4-epoxycyclohexylethyl, 3, 4-epoxycyclohexyl-propyl, 3, 4-epoxynorbornenylethyl, 2- (3, 4-epoxy-3-methylcyclohexyl) -2-methylethyl. The alkoxysilyl group for R7, R8 and R9 is preferably selected from the group consisting of trimethoxysilyl, triethoxysilyl, tripropoxysilyl, triisopropoxysilyl, tricyclopropyloxysilyl, tricyclohexyloxysilyl, dimethoxyethoxysilyl, and methoxydiethoxysilyl.
Especially preferred are the following compounds:
Figure PCTCN2014088194-appb-000003
Among the above unsaturated cyclic isocyanurates, triallyl isocyanurate and diallyl monoglycidyl isocyanurate are more preferable to be used in the present invention.  The reactant (b) is preferably present in an amount of from 1％to 45％, particularly preferred 5％to 35％by weight of all reactants for the organopolysiloxane prepolymer.
Reactant (c)
In the present invention, the reactant (c) is preferably represented by the average structural formula (3) 
R7 eHfSiO (4-e-f) /2                       (3) ,
wherein, R7 is an optionally substituted monovalent organic group which is selected from, as defined above, an alkyl group having from 1 to 20 carbon atoms, an aryl group or arylene group having from 6 to 20 carbon atoms, and the combination thereof； e is a positive number of from 0.7 to 2.1, preferably from 0.9 to 2.1； f is a positive number of from 0.001 to 1.0, preferably from 0.01 to 1.0； and the sum of e+f is from 0.8 to 3, preferably from 1 to 2.5.
Specifically, the reactant (c) may be exemplified by 1, 3-dimethyl-1, 3-diphenyl-disiloxane, 3-(dimethylvinylsiloxy) -1, 1, 5, 5-tetramethyl-3-phenyltrisiloxane, 3-(dimethylvinylsiloxy) -1, 1, 5, 5-tetramethyl-3-methyltrisiloxane, 1, 1, 3, 3-tetramethyl-disiloxane, 1, 1, 5, 5-tetramethyl-3, 3-diphenyltrisiloxane, 1, 1, 7, 7-tetramethyl-3, 5-diphenyltetrasiloxane, 1, 1, 9, 9-tetramethyl-3, 5, 7-triphenylpentasiloxane, 1, 1, 11, 11-tetramethyl-3, 5, 7, 9-tetraphenylhexasiloxane, 1, 1, 3, 3, 5, 5, 7, 7-octamethyltetrasiloxane, 1, 1, 3, 3-tetramethyldisiloxane, and a hydride terminated polydimethylsiloxane.
In one particular embodiment, 1, 1, 5, 5-tetramethyl-3, 3-diphenyltrisiloxane is used as the reactant (c) for the preparation of the organopolysiloxane prepolymer.
The reactant (c) is preferably present in an amount of from 1％to 50％, more preferably 5％to 40％by weight of all reactants for the organopolysiloxane prepolymer.
Hydrosilylation catalyst (I)
The reaction of the above components also involves the use of catalyst for hydrosilylation. According to the present invention, as hydrosilylation catalyst (I) it is possible to use all catalysts which are useful for the addition of Si-bonded hydrogen onto aliphatically unsaturated compounds. Examples of such catalysts are compounds or complexes of precious metals comprising platinum, ruthenium, iridium, rhodium and palladium, such as, for example, platinum halides, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H2PtCl6.6H2O and cyclohexanone, platinum-vinylsiloxane complexes, in particular platinum-divinyltetramethyldisiloxane complexes with or without a content of detectable inorganically bonded halogen, bis (γ-picolin) -platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, dimethylsulfoxide ethylene-platinum (II) dichloride and also reaction products of platinum tetrachloride with olefin and primary amine or secondary amine or primary and secondary amine, such as, for example, the reaction product of platinum tetrachloride dissolved in 1-octene with sec-butylamine. In addition, complexes of iridium with cyclooctadienes, such as, for example, μ-dichlorobis (cyclooctadiene) -diiridium (I) , can also be used in the present invention.
Preferably, the catalyst is a compound or complex of platinum, preferably selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum and 2 ,4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetramethyldisiloxane complex, and the combination thereof, and most preferably platinum-divinyltetramethyldisiloxane complexes.
The hydrosilylation catalyst (I) is used for preparing the organopolysiloxane prepolymer according to the present invention preferably in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, based on the total weight of all reactants.
In one embodiment, the present invention provides an organopolysiloxane prepolymer, which is a reaction product of reactants comprising:
a) from 5％to 80％, preferably 25％to 70％by weight of the reactant (a) ,
b) from 1％to 45％, preferably 5％to 35％by weight of the reactant (b) ,
c) from 1％to 50％, preferably 5％to 40％by weight of the reactant (c) , and
d) from 1 to 500 ppm, preferably 2 to 100 ppm of the hydrosilylation catalyst (I) calculated as the elemental precious metal contained therein,
wherein the percentages by weight and ppm are based on the total weight of all reactants.
The organopolysiloxane prepolymer composition
In another aspect, the present invention provides organopolysiloxane prepolymer compositions, comprising the organopolysiloxane prepolymer according to the present invention.
Besides the components/reactants described above, the organopolysiloxane prepolymer (composition) may also optionally comprise additional components/reactants. Examples of the additional components/reactants include, but are not limited to a curing retarder, a viscosity regulating agent and an adhesion promoter.
The curing retarder may be added to the reactants to control the reaction, and may be selected from the group consisting of aliphatic unsaturated compounds, organic phosphorous compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the combination thereof, and more preferably is selected from 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane, 3-methyl butynol, 1-ethynylcyclohexanol, benzotiazol, tert-butyl hydroperoxide. The curing retarders which can be used for the organopolysiloxane prepolymer are preferably present in an amount of from 0.1 to 1000 mols, more preferably from 1 to 50 mols per mol of the hydrosilylation catalyst (I) .
The viscosity regulating agent may be added when preparing the organopolysiloxane prepolymer. Non-limiting examples are linear, cyclic,  network-type organopolysiloxanes, and organic solvents well known to a person skilled in the art. The specific selection of the viscosity regulating agent will depend on the practical need, and will be easily determined by a skilled artisan.
The adhesion promoter may be added when preparing the organopolysiloxane prepolymer. Non-limiting examples are silane coupling agents, organosilicon compounds containing SiH groups, alkenyl groups, alkoxysilyl groups and epoxy groups, isocyanurate compounds, and combination thereof, and more preferably selected from vinyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, tris- (trimethoxysilylpropyl) isocyanurate, monoallyldiglycidylisocyanurate, and combination thereof. The adhesion promoter which can be used for the organopolysiloxane prepolymer is preferably present in an amount of from less than 10％, more preferably less than 5％by weight of all reactants.
The curable organopolysiloxane composition
Another aspect is directed to a curable organopolysiloxane composition, comprising:
(a) the organopolysiloxane prepolymer according to the present invention,
(b) an organohydrogenpolysiloxane having at least two Si-H group in one molecule, and
(c) a hydrosilylation catalyst (II) .
In the curable organopolysiloxane composition according to the present invention, the component (b) is preferably represented by the average compositional formula (4) :
R7 gHhSiO (4-g-h) /2                                      (4) ,
wherein R7 is a monovalent organic group, independently selected from an alkyl group having from 1 to 20 carbon atoms, an aryl group or arylene groups having from 6 to 20 carbon atoms, and the combination thereof； g is a positive number of from 0.7 to 2.1, preferably from 0.9 to 2.1, h is a positive number of from 0.001 to 1.0, preferably from 0.01 to 1.0, and the sum of g+h is from 0.8 to 3, preferably from 1 to 2.5, wherein at least one of R7 is aryl or arylene.
Preferably, the component (b) is selected from the group consisting of hydride terminated methylhydrosiloxane-phenylmethylsiloxane copolymers, hydride terminated polydimethylphenylsiloxanes, hydride terminated polyphenyl (dimethylsiloxy) siloxanes, hydride terminated polydiphenylsiloxanes, hydride terminated methyl hydrosiloxane-phenylmethylsiloxane copolymers, and combination thereof. More preferably, the component (b) is a hydride terminated polyphenyl (dimethylsiloxy) siloxane commercially available under the trade name of KM-390 or a hydride terminated polydiphenylsiloxane available under the trade name of KM-391 from Wuhan Kemi-Works Chemical.
In one embodiment, the amount of the component (b) of the organopolysiloxane prepolymer is from 1 to 40％, preferably from 5 to 30％by weight of the total amount of components (a) and (b) of the curable organopolysiloxane composition.
In another embodiment, the component (b) of the organopolysiloxane prepolymer is present in an amount so as to provide from 0.1 to 5, preferably 1.0 to 3.0 moles of SiH bonds per one mole of the alkenyl group comprised in components (a) .
The curable organopolysiloxane composition also contains a hydrosilylation catalyst used for hydrosilylation. According to the present invention, as hydrosilylation catalyst (II) , it is possible to use all catalysts which are useful for the addition of Si-bonded hydrogen onto aliphatically unsaturated compounds. The hydrosilylation catalysts (I) and (II) used in the present invention may be the same or different, either singly or in combination. Examples of such catalysts are the same as defined above for the hydrosilylation catalysts (I) .
The hydrosilylation catalyst (II) is used for preparing the curable organopolysiloxane composition according to the present invention preferably in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, based on the total weight of all components.
Besides the components described above, the curable organopolysiloxane composition may also optionally comprise additional components. Examples of the additional components include, but are not limited to a curing retarder, a viscosity  regulating agent, an adhesion promoter, an antioxidant/thermostabilizer, a light stabilizer, a filler, a plasticizer, a dye, a pigment, and combination thereof.
The curing retarder, viscosity regulating agent, adhesion promoter optionally used in the curable organopolysiloxane composition are given as defined above.
The antioxidant or thermostabilizer useful in the curable organopolysiloxane composition includes but is not limited to hindered phenols, phosphites, thioethers, and the examples are tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (2, 4-di-tert-butylphenyl) phosphite, 2, 2'-Methylenebis (4, 6-di-tert-butyl-phenyl) -2-ethylhexyl phosphite, 2, 2-Bis [ [3- (dodecylthio) -1-oxopropoxy] methyl] propane-1, 3-diyl, bis [3- (dodecylthio) propionate] , di (tridecyl) 3, 3'-thiodipropionate, and combination thereof.
If present, the antioxidant is used in the curable organopolysiloxane composition preferably in an amount of 10 to 10,000 ppm, more preferably from 100 to 1,000 ppm, based on the total amount of all components of the curable organopolysiloxane composition.
The light stabilizer useful in the curable organopolysiloxane composition includes but is not limited to hindered amine light stabilizers and ultraviolet absorbents, and the examples are 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2, 2’ -dihydroxy-4, 4’ -dimethoxybenzophenone, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) butane-1, 2, 3, 4-tetracarboxylate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, and combination thereof.
If present, the light stabilizer is preferably used in the curable organopolysiloxane composition in an amount of 10 to 10,000 ppm, more preferably from 100 to 1,000 ppm, based on the total amount of all components of the curable organopolysiloxane composition.
Fillers may also be comprised in the curable organopolysiloxane composition, and may be selected from the group consisting of finely divided silica, calcium carbonate, quartz powder, aluminium hydroxide, zirconium silicate, diatomaceous earth, titanium dioxide, and combination thereof.
The present invention also provides a cured product obtained from the curable organopolysiloxane composition as described above.
According to the present invention, the organopolysiloxane prepolymer, the organopolysiloxane prepolymer composition or the curable organopolysiloxane composition or the cured product can be used in the manufacturing of optical devices, especially light emitting materials, e. g. LEDs applied for instance in general lighting equipment, backlight of mobile phone, tablets, PC, or TV, and light source for automotive. Others uses includes coating, die attach and reflector for LED.
When used as an encapsulant for LEDs, the cured products provide excellent properties in thermal resistance, optical coloration and moisture permeability at the same time. Besides, the cured products exhibit high adhesiveness and toughness.
The following examples are intended to assist one skilled in the art to better understand and practice the present invention. The scope of the invention is not limited by the examples but is defined in the appended claims. All parts and percentages are based on weight unless otherwise stated.
Examples
The preparation of reactant (a) of the organopolysiloxane prepolymer -vinyl phenyl  silicone resin
The vinyl phenyl silicone resin was prepared according to conventional industrial method as below: 63.72 Kg phenyltrimethoxysilane, 10.38 Kg vinyldimethylethoxysilane, 31.50 Kg toluene and 14.04 Kg 0.1M HCl aqueous were pumped into a 50 L glass reactor in this order under stirring. The mixture was placed on an oil bath heat up to 65℃ and kept for 4 hours, and then the volatile compounds was vacuumed to obtain a vinyl phenyl silicone resin as a colorless  clear liquid. The vinyl content of the product is 2.1 mmol/g.
The preparation of prepolymer 1
In a 500mL glass reactor, 100 parts of vinyl phenyl silicone resin as obtained above, 150 parts of triallyl isocyanate (from Tokyo Chemical Industry Co. , LTD. ) , 100 parts of 1, 1, 5, 5, -tetramethyl-3, 3-diphenyltrisiloxane (from Gelest) , and 0.04 parts of platinum divinyltetramethyldisiloxane complex (from Gelest under the trade name of SIP6830.3) were mixed. The mixture was heated under 100℃ for 2 hours, and thus the product (prepolymer 1) was obtained as a colorless clear liquid.
The preparation of prepolymer 2
In a 500mL glass reactor, 100 parts of vinyl phenyl silicone resin as obtained above, 105 parts of diallyl monoglycidyl isocyanulate (from Shikoku Chemicals Corporation) , 55 parts of 1, 1, 5, 5, -tetramethyl-3, 3-diphenyltrisiloxane (from Gelest) , and 0.03 parts of platinum divinyltetramethyldisiloxane complex (from Gelest under the trade name of SIP6830.3) were mixed. The mixture was heated under 100℃ for 2 hours, and thus the product (prepolymer 2) was obtained as a colorless clear liquid.
Example 1
In a planetary mixer, 100 parts of prepolymer 1 as obtained above, 58 parts of hydride terminated polyphenyl- (dimethylsiloxy) siloxane (from Wuhan Kemi-Works Chemical under the trade name of KM-391) , and 0.04 parts of platinum divinyltetramethyldisiloxane complex (from Gelest) were mixed to homogenity under vacuum to prepare a curable composition. The obtained curable composition was cured at 80℃ for 1h and then 150℃ for 5h. The transmittance of the cured product at 400nm was 90％.
Example 2
In a planetary mixer, 100 parts of prepolymer 2 as obtained above, 92 parts of hydride terminated polydiphenylsiloxane (from Wuhan Kemi-Works Chemical under the trade name of KM-390) , and 0.04 parts of platinum divinyltetramethyldisiloxane complex (from Gelest) were mixed to homogenity under vacuum to prepare a  curable composition. The obtained curable composition was cured at 80℃ for 1h and then 150℃ for 5h. The transmittance of the cured product at 400nm was 89％.
Example 3
In a planetary mixer, 100 parts of prepolymer 2 as obtained above, 41 parts of hydride terminated polyphenyl- (dimethylsiloxy) siloxane (KM-391 from Wuhan Kemi-Works Chemical) , and 0.04 parts of platinum divinyltetramethyldisiloxane complex (from Gelest) were mixed to homogenity under vacuum to prepare a curable composition. The obtained curable composition was cured at 80℃ for 1h and then 150℃ for 5h. The transmittance of the cured product at 400nm was 89％.
Comparative Example 1
In a planetary mixer, 100 parts of vinyl phenyl silicone resin as obtained above, 50 parts of hydride terminated polydiphenylsiloxane (KM-390 from Wuhan Kemi-Works Chemical) , and 0.05 parts of platinum divinyltetramethyldisiloxane complex (from Gelest) were mixed to homogenity under vacuum to prepare a curable composition. The obtained curable composition was cured at 80℃ for 1h and then 150℃ for 5h. The transmittance of the cured product at 400nm is 89％.
Comparative Example 2
In a planetary mixer, 100 parts of vinyl phenyl silicone resin as obtained above, 150 parts of triallyl isocyanulate, 100 parts of 1, 1, 5, 5, -tetramethyl-3, 3-diphenyltrisiloxane, 320 parts of hydride terminated polydiphenylsiloxane (KM-390 from Wuhan Kemi-Works Chemical) , and 0.2 parts of Platinum divinyltetramethyldisiloxane complex (from Gelest) were mixed to homogenity under vacuum to prepare a curable composition. The obtained curable composition was cured at 80℃ for 1h and then 150℃ for 5h. The transmittance of the cured product at 400nm is 89％.
Evaluation
Examples 1 to 3 and Comparative Examples 1 and 2 were tested for their performance in luminous maintenance after Sulfur test and the TCT failure test.
The luminous maintenance (％) after Sulfur test was tested as follows:
Each of the curable compositions from Examples 1 to 3 and Comparative Examples 1 and 2 were dispensed in a LED device (5050 size, 1W power consumption) and cured at 80℃ for 1h and at 150℃ for 5h in an oven to prepare a resin sample. The resin sample was put in a container of 3.3L that spreads sulfur powder of 22g all over the bottom surface. The container was kept at 70℃ for 96 hours. Luminous flux was measured by integrating sphere (Otsuka Denshi, HM-9050B) and the measurement was conducted before testing and after 96 hours exposure in sulfur. The measured luminous flux values prior to test and after 96 hours were compared to find the degradation degree. The luminous maintenance (％) after sulfur test was calculated as dividing the luminous flux values prior to test by the luminous flux values after 96 hours. The luminous flux value is typically influenced by the factors including optical coloration, moisture permeability, adhesion and toughness of the cured product.
The failure ratio (％) after thermal cycle test (TCT) was tested as follows:
Each of the curable compositions from Examples 1 to 3 and Comparative Examples 1 and 2 were dispensed in a LED device (3528 size, 0.15W power consumption) and cured at 80℃ for 1h and at 150℃ for 5h in an oven to prepare a resin sample. The sample was subjected to a thermal cycle of -40℃ for 30min and 100℃ for 30min. The cracking or delamination of the sample was visually observed by microscope after 500 cycles. The failure ratio (％) was calculated as dividing the number of cracked or delaminated samples by the total number of samples. The failure ratio (％) after TCT is typically influenced by the thermal resistance of the curable product.
The test results are shown in Table 1 as below.
Table 1: Test results of luminous maintenance after Sulfur test and failure ratio after TCT test
Figure PCTCN2014088194-appb-000004
As can be seen from Table 1, each of the Examples 1 to 3 exhibited excellent performance in both of luminous maintenance after Sulfur test and failure ratio after TCT test.
Although Comparative Example 1 also possessed a failure ratio after TCT test as good as Example 1, the luminous maintenance after Sulfur test of Comparative Example 1 was significantly deteriorated to 60％, which cannot not be accepted in the art. It is believed that the presence of cyclic isocyanurates which provides a triazine structure in the prepolymer product enhanced the stability and reliability of the final cured product in all of optical coloration, moisture permeability and thermal resistance.
Although Comparative Example 2 possessed a luminous maintenance as good as Examples 1-3, the failure ratio after TCT test of Comparative Example 2 was significantly deteriorated to 80％, which cannot be accepted in the art. It is believed that the two preparation steps of prepolymer and curable composition is significantly important to increase the thermal resistance of the cured product.
Therefore, the above results of TCT test and Sulfur test proved that the cured products prepared from the prepolymer and curable composition according to the present invention resulted in a much better long term reliability and a more desired  combined properties of thermal resistance, optical coloration, moisture permeability, adhesion and toughness compared to those from the Comparative Examples.
These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in component. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

Claims (30)

  1. An organopolysiloxane prepolymer, being a reaction product of reactants comprising:
    (a) an organopolysiloxane compound having at least two ethylenically unsaturated double bonds represented by the average compositional formula (1) :
    (R1R2R3SiO1/2) a (R4R5SiO2/2) b (R6SiO3/2) c (SiO4/2) d            (1) ,
    wherein
    at least one of R1 to R6 is an alkenyl group having from 2 to 20 carbon atoms, the others of R1 to R6 independently from each other represent optionally substituted monovalent organic group of 1 to 20 carbon atoms, selected from the group consisting of an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms,
    from 15 to 65 mol％ of R1 to R6 in one molecule of the organopolysiloxane compound are an aromatic group having from 6 to 20 carbon atoms, from 1 to 50 mol％ of R1 to R6 in one molecule of the organopolysiloxane compound are an alkenyl group having from 2 to 20 carbon atoms, and the total mol％ of R1 to R6 in one molecule of the organopolysiloxane compound is 100 mol％,
    the ratio of a/ (a+b+c+d) is from 0.1 to 0.8, the ratio of b/ (a+b+c+d) is from 0 to 0.5, the ratio of c/ (a+b+c+d) is from 0.2 to 0.9, the ratio of d/ (a+b+c+d) is from 0 to 0.2, and the sum of a+b+c+d ＝ 1.0,
    (b) a cyclic isocyanurate having two or more ethylenically unsaturated double bonds which is represented by formula (2) 
    Figure PCTCN2014088194-appb-100001
    wherein
    R7, R8 and R9 independently from each other represent an alkyl group having from 1 to 12 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a monovalent organic group represented by- (CH2) m-X or- (CH2) p-O- (CH2) q-Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X  and Y are selected from the group consisting of an alkenyl group having from 2 to 12 carbon atoms, an epoxy group having from 2 to 12 carbon atoms, and an alkoxysilyl group having from 1 to 12 carbon atoms, and at least two of R7, R8 and R9 contain an carbon-carbon double bond,
    (c) a polyorganohydrogensiloxane compound comprising at least one hydrogen atom directly bonded to a silicon atom, and
    (d) an hydrosilylation catalyst (I) .
  2. The organopolysiloxane prepolymer according to claim 1, wherein at least one of R1 to R6 in the reactant (a) is an alkenyl group having from 2 to 8 carbon atoms, and the others of R1 to R6 are independently from each other selected from an alkyl group having from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, and an aromatic group having from 6 to 14 carbon atoms.
  3. The organopolysiloxane prepolymer according to claim 2, wherein the alkenyl group is selected from the group consisting of vinyl, allyl, methallyl, 1, 1-dimethylallyl, 1-butenyl, 2-butenyl, 1, 3-pentadienyl, 1-hexenyl and 1-octenyl； the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, and octyl； the alkoxyl group is selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy； and the aromatic group is selected from the group consisting of phenyl, biphenyl, 1, 2, 3, 4-tetrahydronaphthyl, naphthyl, anthryl, phenanthryl, 9-fluorenyl, dibenzocycloheptatrienyl.
  4. The organopolysiloxane prepolymer according to any of claims 1 to 3, wherein from 20 to 50 mol％ of R1 to R6 in one molecule of the reactant (a) is an aromatic group having from 6 to 20 carbon atoms, preferably aromatic group having from 6 to 14 carbon atoms, more preferably phenyl.
  5. The organopolysiloxane prepolymer according to any of claims 1 to 4, wherein from 5 to 30mol％ of R1 to R6 in one molecule of the reactant (a) are alkenyl group having from 2 to 20 carbon atoms, preferably alkenyl group having from 2 to 8 carbon atoms, more preferably vinyl or allyl.
  6. The organopolysiloxane prepolymer according to any of claims 1 to 5, wherein in reactant (a) , the ratio of a/ (a+b+c+d) is from 0.2 to 0.6, the ratio of b/ (a+b+c+d) is from 0 to 0.3, the ratio of c/ (a+b+c+d) is from 0.3 to 0.7, the ratio of d/ (a+b+c+d) is from 0 to 0.1, and the sum of a+b+c+d ＝ 1.0.
  7. The organopolysiloxane prepolymer according to any of claims 1 to 6, wherein the reactant (a) is produced by the condensation reaction of at least one aromatic alkoxysilane and at least one alkenyl alkoxysilane, wherein the aromatic group in the aromatic alkoxysilane has from 6 to 20 carbon atoms, preferably from 6 to 12 carbon atoms, the alkenyl group in the alkenyl alkoxysilane has from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms, and the alkoxy group in the aromatic alkoxysilane and alkenyl alkoxysilane has from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms.
  8. The organopolysiloxane prepolymer according to any of claims 1 to 7, wherein the reactant (a) is present in an amount of from 5％ to 80％, preferably from 25％ to 70％ by weight of the total weight of all reactants.
  9. The organopolysiloxane prepolymer according to any of claims 1 to 8, wherein R7, R8, and R9 in the reactant (b) independently from each other represent an alkyl group having from 1 to 6 carbon atoms, an aromatic group having from 6 to 12 carbon atoms, a monovalent organic group represented by- (CH2) m-X or- (CH2) p-O- (CH2) q-Y, in which m is from 0 to 3, p is from 0 to 3, q is from 0 to 3, X and Y are selected from the group consisting of an alkenyl group having from 2 to 8 carbon atoms, an epoxy group having from 2 to 8 carbon atoms, and an alkoxysilyl group having from 1 to 8 carbon atoms.
  10. The organopolysiloxane prepolymer according to claim 9, wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, and octyl； the alkenyl group is selected from the group consisting of vinyl, allyl, methallyl, 1, 1-dimethylallyl, 1-butenyl, 2-butenyl, 1, 3-pentadienyl, 1-hexenyl and 1-octenyl； the epoxy group is selected from the group consisting of  glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, 3, 4-epoxycyclohexylethyl, 3, 4-epoxycyclohexylpropyl, 3, 4-epoxynorbornenylethyl, 2- (3, 4-epoxy-3-methylcyclohexyl) -2-methylethyl； and the alkoxysilyl group is selected from the group consisting of trimethoxysilyl, triethoxysilyl, tripropoxysilyl, triisopropoxysilyl, tricyclopropyloxysilyl, tricyclohexyloxysilyl, dimethoxyethoxysilyl, and methoxydiethoxysilyl.
  11. The organopolysiloxane prepolymer according to any of claims 1 to 10, wherein the reactant (b) is selected from the group consisting of:
    Figure PCTCN2014088194-appb-100002
    and combinations thereof.
  12. The organopolysiloxane prepolymer according to any of claims 1 to 11, wherein the reactant (b) is present in an amount of from 1％ to 45％, preferably from 5％ to 35％ by weight of the total weight of all reactants.
  13. The organopolysiloxane prepolymer according to any of claims 1 to 12, wherein the reactant (c) is represented by the average compositional formula (3) :
    R7 eHfSiO (4-e-f) /2                                (3) ,
    wherein R7 is an optionally substituted monovalent organic group, selected from an alkyl group having from 1 to 20 carbon atoms, an aryl group or arylene group having from 6 to 20 carbon atoms, and the combination thereof； e is a positive number of from 0.7 to 2.1, f is a positive number of from 0.001 to 1.0, and the sum of e+f is from 0.8 to 3.
  14. The organopolysiloxane prepolymer according to any of claims 1 to 13, wherein the reactant (c) is selected from the group consisting of 1, 3-dimethyl-1, 3-diphenyl-disiloxane,
    3- (dimethylvinylsiloxy) -1, 1, 5, 5-tetramethyl-3-phenyltrisiloxane,
    3- (dimethylvinylsiloxy) -1, 1, 5, 5-tetramethyl-3-methyltrisiloxane,
    1, 1, 3, 3-tetramethyl-disiloxane, 1, 1, 5, 5-tetramethyl-3, 3-diphenyltrisiloxane,
    1, 1, 7, 7-tetramethyl-3, 5-diphenyltetrasiloxane,
    1, 1, 9, 9-tetramethyl-3, 5, 7-triphenylpentasiloxane,
    1, 1, 11, 11-tetramethyl-3, 5, 7, 9-tetraphenylhexasiloxane,
    1, 1, 3, 3, 5, 5, 7, 7-octamethyltetrasiloxane, 1, 1, 3, 3-tetramethyldisiloxane, a hydride terminated polydimethylsiloxane, and combination thereof.
  15. The organopolysiloxane prepolymer according to any of claims 1 to 14, wherein the reactant (c) is present in an amount of from 1％ to 50％, preferably from 5％ to 40％ by weight of the total weight of all reactants.
  16. The organopolysiloxane prepolymer according to any of claims 1 to 15, wherein the hydrosilylation catalyst (I) comprises elemental precious metal, and is selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum and 2, 4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetramethyldisiloxane complex, and the combination thereof.
  17. The organopolysiloxane prepolymer according to any of claims 1 to 16, wherein  hydrosilylation catalyst (I) is present in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, based on the total weight of all reactants.
  18. The organopolysiloxane prepolymer according to claim 1, being a reaction product of reactants comprising:
    a) from 5％ to 80％, preferably 25％ to 70％ by weight of the reactant (a) ,
    b) from 1％ to 45％, preferably 5％ to 35％ by weight of the reactant (b) ,
    c) from 1％ to 50％, preferably 5％ to 40％ by weight of the reactant (c) , and
    d) from 1 to 500 ppm, preferably 2 to 100 ppm of the hydrosilylation catalyst (I) calculated as the elemental precious metal contained therein,
    wherein the percentages by weight and ppm are based on the total weight of all reactants.
  19. An organopolysiloxane prepolymer composition, comprising the organopolysiloxane prepolymer according to any of claims 1 to 18.
  20. The organopolysiloxane prepolymer composition according to claim 19, further comprising additional components selected from the group consisting of a curing retarder, a viscosity regulating agent, an adhesion promoter, and combination thereof.
  21. A curable organopolysiloxane composition, comprising:
    (a) the organopolysiloxane prepolymer according to any of claims 1 to 18,
    (b) an organohydrogenpolysiloxane having at least two Si-H group in one molecule, and
    (c) a hydrosilylation catalyst (II) .
  22. The curable organopolysiloxane composition according to claim 21, wherein the component (b) is represented by the average compositional formula (4) :
    R7 gHhSiO (4-g-h) /2                                (4) ,
    wherein R7 is a monovalent organic group, independently selected from an alkyl group having from 1 to 20 carbon atoms, an aryl group or arylene group having from 6 to 20 carbon atoms, and the combination thereof； g is a positive number of from 0.7 to 2.1, preferably from 0.9 to 2.1, h is a positive number of from 0.001 to  1.0, preferably from 0.01 to 1.0, and the sum of g+h is from 0.8 to 3, preferably from 1 to 2.5, wherein at least one of R7 is aryl or arylene.
  23. The curable organopolysiloxane composition according to claim 21 or 22, wherein the component (b) is selected from the group consisting of hydride terminated methylhydrosiloxane-phenylmethylsiloxane copolymers, hydride terminated polydimethylphenylsiloxanes, hydride terminated polyphenyl (dimethylsiloxy) siloxanes, hydride terminated polydiphenylsiloxanes, hydride terminated methyl hydrosiloxane-phenylmethylsiloxane copolymers, and combination thereof.
  24. The curable organopolysiloxane composition according to any of claims 21 to 23, wherein the amount of the component (b) of the organopolysiloxane prepolymer is from 1 to 40％ by weight of the total amount of components (a) and (b) of the curable organopolysiloxane composition.
  25. The curable organopolysiloxane composition according to any of claims 21 to 24, wherein the hydrosilylation catalyst (II) is selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum, and 2, 4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetramethyldisiloxane complex, and the combination thereof.
  26. The curable organopolysiloxane composition according to any of claims 21 to 25, wherein the hydrosilylation catalyst (II) is present in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, based on the total weight of all components.
  27. The curable organopolysiloxane composition according to claim 21, comprising components (b) in an amount of providing from 0.1 to 5, preferably 1.0 to 3.0 moles of Si-H groups per one mole of the alkenyl group comprised in components (a) .
  28. A cured product of the curable organopolysiloxane composition according to any of claims 21 to 27.
  29. The use of the cured product according to claim 28 as an encapsulant for light emitting materials.
  30. The use of the organopolysiloxane prepolymer according to any of claims 1 to 18 or the organopolysiloxane prepolymer composition according to any of claims 19 to 20 or the curable organopolysiloxane composition according to any of claims 21 to 27 or the cured product according to claim 28 in the manufacturing of optical devices.
PCT/CN2014/088194 2014-10-09 2014-10-09 An organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same WO2016054781A1 (en)

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KR102467690B1 (en) * 2020-08-19 2022-11-17 주식회사 케이씨씨실리콘 Polysiloxane composition for optical use and reflective materials for optical semiconductor comprising the same

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