WO2011111945A2 - A preparation method of silicone composition having high refractive index for light emitting diode device - Google Patents

A preparation method of silicone composition having high refractive index for light emitting diode device Download PDF

Info

Publication number
WO2011111945A2
WO2011111945A2 PCT/KR2011/001434 KR2011001434W WO2011111945A2 WO 2011111945 A2 WO2011111945 A2 WO 2011111945A2 KR 2011001434 W KR2011001434 W KR 2011001434W WO 2011111945 A2 WO2011111945 A2 WO 2011111945A2
Authority
WO
WIPO (PCT)
Prior art keywords
organopolysiloxane
silicone composition
high refractive
preparation
preparing
Prior art date
Application number
PCT/KR2011/001434
Other languages
French (fr)
Other versions
WO2011111945A3 (en
Inventor
Seung Kwang Seo
Seung Hyun Kang
Su Jin Lee
Original Assignee
Kcc Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kcc Corporation filed Critical Kcc Corporation
Publication of WO2011111945A2 publication Critical patent/WO2011111945A2/en
Publication of WO2011111945A3 publication Critical patent/WO2011111945A3/en

Links

Classifications

    • 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
    • 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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a method for preparing a high refractive organopolysiloxane which is used for brightness improvement, device protection and adhesion of light emitting diode (LED) devices. More specifically, contrary to conventional methods using an excessive amount of catalyst for equilibrium reaction, the present invention relates to a method for preparing a high refractive organopolysiloxane through condensation reactions using a slight amount of catalyst, by which the reduction of ion content, easy removal of silanol groups and saving of production time can be achieved simultaneously; and a silicone composition for light emitting diode (LED) devices comprising the high refractive organopolysiloxane prepared by the method.
  • LED light emitting diode
  • Epoxy resins are generally used as a sealing material for LED. Recently, silicone materials are suggested as an alternative due to the increasing need for heat resistance according to higher brightness and higher output of LED devices or modules.
  • silicone resins are well known as having good heat resistance, cold resistance, electrical insulation, weatherability, water repellency, transparency and the like, and so are widely used in various fields such as electric/electronic devices, OA devices, cars, precision devices, construction materials, etc.
  • transparent organic materials are particularly expected to replace inorganic glass materials in many fields such as optical lens because of their good processability, light weight, low cost and impact resistance.
  • organic resin materials are exposed to high temperature and high light intensity and thus the development of transparent organic resin material having better heat resistance and light resistance is further required.
  • transparent organic resin materials silicone resins have good heat resistance, UV resistance and transparency. Furthermore, even after long term use of silicone resins, the yellowing phenomenon due to epoxy does not occur, the transmission ratio is not lowered substantially, and the physical properties are hardly deteriorated.
  • silicone resins are expected to be used as materials for optical parts.
  • the addition-reaction curable silicone resin composition disclosed in Japanese Patent Publication No. 3344286 B is solvent-free type, and thus shows better moldability than solvent type, condensation curable silicone varnishes, and is advantageous in terms of environment since it does not contain solvent substantially.
  • 2002-265787 A comprises a resin with high hardness and high transparency obtained by adding and curing a specific organopolysiloxane having phenyl groups and alkenyl groups and a specific organohydrogenpolysiloxane having phenyl groups, since it is important to increase crrosslinking density of siloxanes and to improve the strength of cured product, particularly flexural strength and hardness, by ⁇ - ⁇ interaction between aromatic rings.
  • high refractive, reactive organopolysiloxane examples include the following structures 1) to 9) wherein Vi represents vinyl group, Ph represents phenyl group and Me represents methyl group (the same definitions are applied hereinafter).
  • conventional methods for preparing an organopolysiloxane containing phenyl groups comprise a hydrolysis reaction of chlorosilane having various phenyl groups, water and alcohol, and a subsequent removal of residual ions by using water.
  • such methods have a defect of very high silanol (Si-OH) content.
  • an alkali catalyst is added to the hydrolysis reaction product to conduct an equilibrium reaction.
  • a large amount of alkali (or alkaline earth) catalyst should be added for equilibrium reaction. This is particularly required in case of organopolysiloxanes having methylphenyl only such as the above 1) and 4) structures.
  • a large amount of ions caused from catalyst or neutralizing agent remains in the final product, which may generate a problem in durability of the final cured product for light emitting diodes and thus it is necessary to employ a complicated procedure for minimizing the ion content.
  • the present invention has an object of providing a method for preparing a high refractive organopolysiloxane through condensation reaction, by which the reduction of ion content, easy removal of silanol groups and saving of production time can be achieved simultaneously.
  • the present invention provides a method for preparing an organopolysiloxane, comprising the steps of: (1) conducting a condensation reaction of compounds of the following formula 1 by using an alkali condensation catalyst; and (2) conducting a condensation reaction of a compound of the following formula 2 with the product obtained in step (1) to prepare an organopolysiloxane of the following formula 3.
  • each of R 1 and R 2 is independently hydrogen; C 1 -C 18 alkyl which is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or octadecyl; C 5 -C 8 cycloalkyl which is, for example, cyclopentyl or cyclohexyl; C 6 -C 10 aryl which is, for example, phenyl, tolyl, xylyl or naphthyl; C 6 -C 10 arylC 1 -C 6 alkyl which is, for example, benzyl, phenethyl or 3-phenylpropyl; C 1 -C 6 alkyl substituted with 1 to 3 halogens which is, for example, 3,3,3-trifluoropropyl or 3-chloro
  • each of p, q and r is independently an integer of 0 to 1000.
  • R 1 and R 2 are the same as defined in formula 1,
  • R 3 is C 1 -C 6 alkyl substituted with 1 to 3 halogens which is, for example, 3-chloropropyl; halogen which is, for example, chloro; or C 1 -C 6 alkoxy, and
  • R 4 is hydrogen; C 1 -C 18 alkyl which is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or octadecyl; C 5 -C 8 cycloalkyl which is, for example, cyclopentyl or cyclohexyl; C 6 -C 10 aryl which is, for example, phenyl, tolyl, xylyl or naphthyl; C 6 -C 10 arylC 1 -C 6 alkyl which is, for example, benzyl, phenethyl or 3-phenylpropyl; C 1 -C 6 alkyl substituted with 1 to 3 halogens which is, for example, 3,3,3-trifluoropropyl or 3-chloropropyl; or C
  • R 1 , R 2 , R 3 , R 4 , p, q and r are the same as defined in formulas 1 and 2.
  • alkali metal hydroxide is preferably used in an amount of 1 ⁇ 30ppm based on the total weight of reactants.
  • step (1) the condensation reaction of step (1) is preferably conducted at 60°C to 200°C for 2 to 3 hours.
  • Another aspect of the present invention provides a silicone composition comprising an organopolysiloxane prepared by the above method.
  • the silicone composition preferably has a refractive index of 1.40 or higher, more preferably 1.40 to 1.53, to wavelength of 589nm at 25°C; and provides a cured product preferably having a durometer (Shore D) hardness of 30 or higher, more preferably 30 to 80, after curing at 150 °C for 1 hour.
  • the cured product preferably has a transmission ratio of 85% or more, more preferably 85% to 99%, for visible light (400 to 700nm); and preferably has a water absorption ratio of 12g/m 2 or less after keeping it at 38°C for 24 hours.
  • the silicone composition can be used for sealing a light emitting diode (LED) or for an optical lens.
  • LED light emitting diode
  • the present invention is characterized in preparing a compound of a structure such as the following 1) to 9) with using a slight amount of alkali catalyst and using a water-soluble acid as a neutralizing agent, by which the ion content can be simply controlled below 5ppm even by 2 ⁇ 3 times of water washing.
  • the present invention is characterized in preparing organopolysiloxanes of various structures by capping or coupling methylphenyl-organopolysiloxane having terminal silanol groups with vinyldimethylchlorosilane, dimethylchlorosilane, methyldichlorosilane, vinylmethyldichlorosilane or trimethylchlorosilane in order to provide high refractive organopolysiloxanes with a reactive group such as vinyl, hydrogen, etc.
  • An embodiment of the present invention provides a high refractive, reactive organopolysiloxane for a light emitting diode (LED) prepared by such a method as explained below, and a silicone composition comprising the same for LED devices.
  • LED light emitting diode
  • an acid catalyst is necessarily used since Si-H groups would disappear and hydrogen gas would be generated although such a problem would not occur when vinyl group is contained.
  • Such an acid catalyst is used in amount of from 1000ppm at least up to 3%, by which ion content in the final product may be problematic.
  • a compound of the following formula 4 is hydrolyzed to generate a hydrolysate (i.e., hydrolysis product) terminated with silanol group.
  • each of R 1 and R 2 is independently hydrogen; C 1 -C 18 alkyl which is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or octadecyl; C 5 -C 8 cycloalkyl which is, for example, cyclopentyl or cyclohexyl; C 6 -C 10 aryl which is, for example, phenyl, tolyl, xylyl or naphthyl; C 6 -C 10 arylC 1 -C 6 alkyl which is, for example, benzyl, phenethyl or 3-phenylpropyl; C 1 -C 6 alkyl substituted with 1 to 3 halogens which is, for example, 3,3,3-trifluoropropyl or 3-chloro
  • R 1 and R 2 may be different from each other in the same molecular structure
  • R 3 is C 1 -C 6 alkyl substituted with 1 to 3 halogens which is, for example, 3-chloropropyl; halogen which is, for example, chloro; or C 1 -C 6 alkoxy.
  • silanes of formula 4 can be hydrolyzed, and subjected to condensation reaction to produce ⁇ , ⁇ -dimethylhydroxysilyl-methylphenylpolysiloxane such as formula 1.
  • step (1) of the preparation method of the present invention an alkali catalyst is added to a compound of formula 1 and a condensation reaction is conducted to prepare a high viscous product of condensed ⁇ , ⁇ -dimethylhydroxysilyl-methylphenylpolysiloxane.
  • the alkali catalyst is alkali metal hydroxide and it is preferably used in an amount of 1ppm to 1000ppm and more preferably 5ppm to 30ppm based on the total weight of reactants, by which the reaction rate can be maintained properly and the discoloration or white cloudy phenomenon can be prevented.
  • the values of p, q and r may independently be an integer of 0 to 100,000.
  • step (2) of the preparation method of the present invention the terminal silanol group of the high viscous product obtained as above is condensed with a silane compound of the above formula 2, by which the terminal silanol group is removed and unreactive or reactive group is provided, and a high refractive organopolysiloxane of the above formula 3 can be obtained.
  • the method for preparing a high refractive organopolysiloxane according to the present invention utilizes a condensation reaction using a slight amount of catalyst, and thus can reduce the steps and time for the preparation as compared with conventional methods using an equilibrium reaction via addition of excessive amount of catalyst.
  • the present invention is characterized in that ion content can be controlled easily and thus no separate device, manpower and time are necessary to further remove ions, which can contribute to the improvement in properties of a silicone composition for light emitting diodes and reduction of cost for producing light emitting diode devices.
  • a high refractive organopolysiloxane prepared according to the present invention is highly refractive, transparent, hard, heat-resistant and light-transmissible, and even after exposure to high temperature-high humidity environment for a long time and returning to room temperature, the cured product does not show any white cloudy phenomenon. Furthermore, its ion content and silanol content can be controlled easily.
  • the prepared organopolysiloxane solution was stripped at 120°C under 10 torr or less for 2 hours to obtain ⁇ , ⁇ -dimethylhydroxysilyl-methylphenylpolysiloxane having viscosity of 600 cP and 50 mol% of phenyl group with respect to silicon atoms in one molecule, based on 100 parts by weight of organopolysiloxane.
  • a flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of dimethylhydroxysilyl-methylphenylpolysiloxane obtained above and purged with nitrogen for 30 minutes to make nitrogen atmosphere therein.
  • the temperature in the flask was then elevated to 120°C with continuous purging with nitrogen, and 10ppm (0.01g) of potassium hydroxide was added thereto.
  • the viscosity was increased gradually as the reaction proceeded.
  • hydrochloric acid was added in an amount of 1.5 times of moles of potassium hydroxide, and the resulting mixture was stirred for 1 hour and neutralized.
  • a flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of ⁇ , ⁇ -dimethylhydroxysilyl-methylphenylpolysiloxane obtained above and purged with nitrogen for 30 minutes to make nitrogen atmosphere therein.
  • the temperature in the flask was then elevated to 120°C with continuous purging with nitrogen, and 10ppm (0.01g) of potassium hydroxide was added thereto.
  • the viscosity was increased gradually as the reaction proceeded.
  • hydrochloric acid was added in an amount of 1.5 times of moles of potassium hydroxide, and the resulting mixture was stirred for 1 hour and neutralized.
  • a flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of dimethylhydroxysilyl-methylphenylpolysiloxane obtained above, and purged with nitrogen for 30 minutes with heating to 40°C, to make nitrogen atmosphere therein. After sealing the flask, 1g of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane was added thereto and as a catalyst, trifluoromethanesulfonic acid was added in an amount corresponding to 1000ppm of reactants.
  • N.D. means no detection
  • tr means a tracing amount which was lower than 0.05ppm, the detection limit of ion content by the used ion analysis instrument.
  • Examples 1 to 3 according to the preparation process of the present invention showed 13.5 hours of the average preparation time, saving about 7.5 hours as compared with 21 hours for the prior art.
  • the ion contents of the high refractive organopolysiloxanes prepared by the preparation process of the present invention were remarkably lower than those of the prior art.
  • the known method of prior art may reduce the ion content by employing an additional re-treatment procedure to control the ion content, but the preparation time further increases thereby.
  • the sealing material was injected into 0.2mm space between two glass sheets and cured at 150°C for 1 hour to prepare a cured silicone sample cell.
  • the light transmission property of the cured silicone body was measured at 450nm wavelength and 25°C by using an automatic spectrophotometer with visible light of arbitrary wavelength (400 ⁇ 700nm).
  • the refractive index to a visible light was measured at 25°C by using an Abbe refractometer.
  • the sealing material was molded under pressure at 150°C for 1 hour to form a sheet of the cured silicone body, and its hardness was measured according to JIS K6253 by using a hardness tester of A type or D type.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Led Device Packages (AREA)

Abstract

The present invention relates to a method for preparing a high refractive organopolysiloxane through condensation reactions. More specifically, the present invention relates to a method for preparing a high refractive organopolysiloxane through condensation reactions using a slight amount of catalyst, by which the reduction of ion content, easy removal of silanol groups and saving of production time can be achieved simultaneously; and a silicone composition for light emitting diode (LED) devices comprising the high refractive organopolysiloxane prepared by the method.

Description

A PREPARATION METHOD OF SILICONE COMPOSITION HAVING HIGH REFRACTIVE INDEX FOR LIGHT EMITTING DIODE DEVICE
The present invention relates to a method for preparing a high refractive organopolysiloxane which is used for brightness improvement, device protection and adhesion of light emitting diode (LED) devices. More specifically, contrary to conventional methods using an excessive amount of catalyst for equilibrium reaction, the present invention relates to a method for preparing a high refractive organopolysiloxane through condensation reactions using a slight amount of catalyst, by which the reduction of ion content, easy removal of silanol groups and saving of production time can be achieved simultaneously; and a silicone composition for light emitting diode (LED) devices comprising the high refractive organopolysiloxane prepared by the method.
Epoxy resins are generally used as a sealing material for LED. Recently, silicone materials are suggested as an alternative due to the increasing need for heat resistance according to higher brightness and higher output of LED devices or modules.
In general, silicone resins are well known as having good heat resistance, cold resistance, electrical insulation, weatherability, water repellency, transparency and the like, and so are widely used in various fields such as electric/electronic devices, OA devices, cars, precision devices, construction materials, etc.
Recently, transparent organic materials are particularly expected to replace inorganic glass materials in many fields such as optical lens because of their good processability, light weight, low cost and impact resistance. In addition, according to the trend of downsizing optical parts and increasing brightness of light source, organic resin materials are exposed to high temperature and high light intensity and thus the development of transparent organic resin material having better heat resistance and light resistance is further required. Among such transparent organic resin materials, silicone resins have good heat resistance, UV resistance and transparency. Furthermore, even after long term use of silicone resins, the yellowing phenomenon due to epoxy does not occur, the transmission ratio is not lowered substantially, and the physical properties are hardly deteriorated. The advantages as such over other organic resin materials, silicone resins are expected to be used as materials for optical parts.
Among silicone resin materials, the addition-reaction curable silicone resin composition disclosed in Japanese Patent Publication No. 3344286 B is solvent-free type, and thus shows better moldability than solvent type, condensation curable silicone varnishes, and is advantageous in terms of environment since it does not contain solvent substantially. In addition, the silicone resin composition disclosed in Japanese Patent Application Publication No. 2002-265787 A comprises a resin with high hardness and high transparency obtained by adding and curing a specific organopolysiloxane having phenyl groups and alkenyl groups and a specific organohydrogenpolysiloxane having phenyl groups, since it is important to increase crrosslinking density of siloxanes and to improve the strength of cured product, particularly flexural strength and hardness, by π-π interaction between aromatic rings.
In order to prepare a high refractive cured product for light emitting diodes, it is necessary to prepare a reactive organopolysiloxane. Examples of high refractive, reactive organopolysiloxane include the following structures 1) to 9) wherein Vi represents vinyl group, Ph represents phenyl group and Me represents methyl group (the same definitions are applied hereinafter).
1) ViMe2SiO(MePhSiO)nSiMe2Vi
2) ViMe2SiO(MePhSi)m(MeViSiO)nSiMe2Vi
3) ViMe2SiO(MePhSiO)m(MeViSiO)nSiMe3
4) Me3SiO(MePhSiO)m(MeViSiO)nSiMe3
5) HMe2SiO(MePhSiO)nSiMe2H
6) HMe2SiO(MePhSiO)m(MeHSiO)nSiMe2H
7) HMe2SiO(MePhSiO)m(MeHSiO)nSiMe3
8) Me3SiO(MePhSiO)m(MeViSiO)nSiMe3
9) Me3SiO(MePhSiO)m(MeHSiO)nSiMe3
Generally, conventional methods for preparing an organopolysiloxane containing phenyl groups (e.g., Japanese Patent Application Publication No. 2006-041927 A) comprise a hydrolysis reaction of chlorosilane having various phenyl groups, water and alcohol, and a subsequent removal of residual ions by using water. However, such methods have a defect of very high silanol (Si-OH) content.
To remove silanol groups, an alkali catalyst is added to the hydrolysis reaction product to conduct an equilibrium reaction. In such a case, however, a large amount of alkali (or alkaline earth) catalyst should be added for equilibrium reaction. This is particularly required in case of organopolysiloxanes having methylphenyl only such as the above 1) and 4) structures. In such a case, a large amount of ions caused from catalyst or neutralizing agent remains in the final product, which may generate a problem in durability of the final cured product for light emitting diodes and thus it is necessary to employ a complicated procedure for minimizing the ion content.
<PRIOR ART PUBLICATIONS>
<PATENT PUBLICATIONS>
Japanese Patent Publication No. 3344286 B
Japanese Patent Application Publication No. 2002-265787 A
Japanese Patent Application Publication No. 2006-041927 A
To resolve the problems of prior arts as explained above, contrary to conventional methods through equilibrium reaction, the present invention has an object of providing a method for preparing a high refractive organopolysiloxane through condensation reaction, by which the reduction of ion content, easy removal of silanol groups and saving of production time can be achieved simultaneously.
To achieve the object as explained above, the present invention provides a method for preparing an organopolysiloxane, comprising the steps of: (1) conducting a condensation reaction of compounds of the following formula 1 by using an alkali condensation catalyst; and (2) conducting a condensation reaction of a compound of the following formula 2 with the product obtained in step (1) to prepare an organopolysiloxane of the following formula 3.
[Formula 1]
Figure PCTKR2011001434-appb-I000001
In the above formula 1,
each of R1 and R2 is independently hydrogen; C1-C18alkyl which is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or octadecyl; C5-C8cycloalkyl which is, for example, cyclopentyl or cyclohexyl; C6-C10aryl which is, for example, phenyl, tolyl, xylyl or naphthyl; C6-C10arylC1-C6alkyl which is, for example, benzyl, phenethyl or 3-phenylpropyl; C1-C6alkyl substituted with 1 to 3 halogens which is, for example, 3,3,3-trifluoropropyl or 3-chloropropyl; or C2-C8alkenyl which is, for example, vinyl, allyl, butenyl, pentenyl or hexenyl, and
each of p, q and r is independently an integer of 0 to 1000.
[Formula 2]
Figure PCTKR2011001434-appb-I000002
In the above formula 2,
R1 and R2 are the same as defined in formula 1,
R3 is C1-C6alkyl substituted with 1 to 3 halogens which is, for example, 3-chloropropyl; halogen which is, for example, chloro; or C1-C6alkoxy, and
R4 is hydrogen; C1-C18alkyl which is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or octadecyl; C5-C8cycloalkyl which is, for example, cyclopentyl or cyclohexyl; C6-C10aryl which is, for example, phenyl, tolyl, xylyl or naphthyl; C6-C10arylC1-C6alkyl which is, for example, benzyl, phenethyl or 3-phenylpropyl; C1-C6alkyl substituted with 1 to 3 halogens which is, for example, 3,3,3-trifluoropropyl or 3-chloropropyl; or C2-C8alkenyl which is, for example, vinyl, allyl, butenyl, pentenyl or hexenyl.
[Formula 3]
Figure PCTKR2011001434-appb-I000003
In the above formula 3,
R1, R2, R3, R4, p, q and r are the same as defined in formulas 1 and 2.
In the above method, as the alkali condensation catalyst, alkali metal hydroxide is preferably used in an amount of 1~30ppm based on the total weight of reactants.
In the above method, the condensation reaction of step (1) is preferably conducted at 60℃ to 200℃ for 2 to 3 hours.
Another aspect of the present invention provides a silicone composition comprising an organopolysiloxane prepared by the above method.
The silicone composition preferably has a refractive index of 1.40 or higher, more preferably 1.40 to 1.53, to wavelength of 589nm at 25℃; and provides a cured product preferably having a durometer (Shore D) hardness of 30 or higher, more preferably 30 to 80, after curing at 150 ℃ for 1 hour. In addition, the cured product preferably has a transmission ratio of 85% or more, more preferably 85% to 99%, for visible light (400 to 700nm); and preferably has a water absorption ratio of 12g/m2 or less after keeping it at 38℃ for 24 hours.
The silicone composition can be used for sealing a light emitting diode (LED) or for an optical lens.
The present invention is explained in detail below.
Without limitation, the present invention is characterized in preparing a compound of a structure such as the following 1) to 9) with using a slight amount of alkali catalyst and using a water-soluble acid as a neutralizing agent, by which the ion content can be simply controlled below 5ppm even by 2~3 times of water washing. In addition, the present invention is characterized in preparing organopolysiloxanes of various structures by capping or coupling methylphenyl-organopolysiloxane having terminal silanol groups with vinyldimethylchlorosilane, dimethylchlorosilane, methyldichlorosilane, vinylmethyldichlorosilane or trimethylchlorosilane in order to provide high refractive organopolysiloxanes with a reactive group such as vinyl, hydrogen, etc.
1) ViMe2SiO(MePhSiO)nSiMe2Vi
2) ViMe2SiO(MePhSi)m(MeViSiO)nSiMe2Vi
3) ViMe2SiO(MePhSiO)m(MeViSiO)nSiMe3
4) Me3SiO(MePhSiO)m(MeViSiO)nSiMe3
5) HMe2SiO(MePhSiO)nSiMe2H
6) HMe2SiO(MePhSiO)m(MeHSiO)nSiMe2H
7) HMe2SiO(MePhSiO)m(MeHSiO)nSiMe3
8) Me3SiO(MePhSiO)m(MeViSiO)nSiMe3
9) Me3SiO(MePhSiO)m(MeHSiO)nSiMe3
An embodiment of the present invention provides a high refractive, reactive organopolysiloxane for a light emitting diode (LED) prepared by such a method as explained below, and a silicone composition comprising the same for LED devices.
Generally, in case of dimethylpolysiloxane, even a slight amount of alkali catalyst can conduct an equilibrium reaction at a temperature of 120℃ or higher. It is the same as in the cases of dimethyl-methylphenyl copolymer and dimethyl-diphenyl copolymer. However, in case of organopolysiloxanes with a main chain consisting of methylphenyl only such as the above 1) or 4) structure, equilibrium reactions do not occur with a slight amount of catalyst (< 20ppm) even at the temperature of 250℃. Furthermore, in case of organopolysiloxanes containing reactive hydrogens, an acid catalyst is necessarily used since Si-H groups would disappear and hydrogen gas would be generated although such a problem would not occur when vinyl group is contained. Such an acid catalyst is used in amount of from 1000ppm at least up to 3%, by which ion content in the final product may be problematic.
The preparation method according to an embodiment of the present invention is explained in detail below.
First, a compound of the following formula 4 is hydrolyzed to generate a hydrolysate (i.e., hydrolysis product) terminated with silanol group.
[Formula 4]
Figure PCTKR2011001434-appb-I000004
In the above formula 4,
each of R1 and R2 is independently hydrogen; C1-C18alkyl which is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or octadecyl; C5-C8cycloalkyl which is, for example, cyclopentyl or cyclohexyl; C6-C10aryl which is, for example, phenyl, tolyl, xylyl or naphthyl; C6-C10arylC1-C6alkyl which is, for example, benzyl, phenethyl or 3-phenylpropyl; C1-C6alkyl substituted with 1 to 3 halogens which is, for example, 3,3,3-trifluoropropyl or 3-chloropropyl; or C2-C8alkenyl which is, for example, vinyl, allyl, butenyl, pentenyl or hexenyl,
R1 and R2 may be different from each other in the same molecular structure, and
R3 is C1-C6alkyl substituted with 1 to 3 halogens which is, for example, 3-chloropropyl; halogen which is, for example, chloro; or C1-C6alkoxy.
One or more of silanes of formula 4 can be hydrolyzed, and subjected to condensation reaction to produce α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane such as formula 1.
In step (1) of the preparation method of the present invention, an alkali catalyst is added to a compound of formula 1 and a condensation reaction is conducted to prepare a high viscous product of condensed α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane. In this step, the alkali catalyst is alkali metal hydroxide and it is preferably used in an amount of 1ppm to 1000ppm and more preferably 5ppm to 30ppm based on the total weight of reactants, by which the reaction rate can be maintained properly and the discoloration or white cloudy phenomenon can be prevented. In the high viscous product obtained after the condensation reaction, the values of p, q and r may independently be an integer of 0 to 100,000.
In step (2) of the preparation method of the present invention, the terminal silanol group of the high viscous product obtained as above is condensed with a silane compound of the above formula 2, by which the terminal silanol group is removed and unreactive or reactive group is provided, and a high refractive organopolysiloxane of the above formula 3 can be obtained.
By using the method as explained above, it is possible to prepare a high refractive organopolysiloxane having an initial ion content of 5 to 10ppm which may be easily reduced to 5ppm or less by 2 to 3 times of simple water washing.
The method for preparing a high refractive organopolysiloxane according to the present invention utilizes a condensation reaction using a slight amount of catalyst, and thus can reduce the steps and time for the preparation as compared with conventional methods using an equilibrium reaction via addition of excessive amount of catalyst. In particular, the present invention is characterized in that ion content can be controlled easily and thus no separate device, manpower and time are necessary to further remove ions, which can contribute to the improvement in properties of a silicone composition for light emitting diodes and reduction of cost for producing light emitting diode devices. Concretely, a high refractive organopolysiloxane prepared according to the present invention is highly refractive, transparent, hard, heat-resistant and light-transmissible, and even after exposure to high temperature-high humidity environment for a long time and returning to room temperature, the cured product does not show any white cloudy phenomenon. Furthermore, its ion content and silanol content can be controlled easily.
The present invention is explained in more detail by the following Examples and Comparative Examples. However, the scope of the present invention is not limited by them.
Example 1
<Preparation of α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane>
To a flask containing a mixture of 100g of toluene and 161.4g of water with stirring at 5℃ or less, 100g of methylphenyldichlorosilane was added dropwise slowly so that the temperature in the flask might not exceed 30℃, and was hydrolyzed. Then, the resulting mixture was polymerized at 80℃ for additional 1 hour.
After the polymerization, stirring was stopped and the resulting mixture was kept in a stationary state to separate layers. The waste aqueous layer (HCl+H2O) was isolated from the flask, and the same amount of water was added to the flask for water washing. The water washing procedure was repeated until the resulting waste aqueous layer became neutral. After removing the last waste aqueous layer, a toluene solution of methylphenylorganopolysiloxane having terminal silanol group was prepared. The prepared organopolysiloxane solution was stripped at 120℃ under 10 torr or less for 2 hours to obtain α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane having viscosity of 600 cP and 50 mol% of phenyl group with respect to silicon atoms in one molecule, based on 100 parts by weight of organopolysiloxane.
<Preparation of α,ω-vinyldimethylsilyl-methylphenylpolysiloxane>
A flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of dimethylhydroxysilyl-methylphenylpolysiloxane obtained above and purged with nitrogen for 30 minutes to make nitrogen atmosphere therein. The temperature in the flask was then elevated to 120℃ with continuous purging with nitrogen, and 10ppm (0.01g) of potassium hydroxide was added thereto. The viscosity was increased gradually as the reaction proceeded. At the viscosity of 16000 cP, hydrochloric acid was added in an amount of 1.5 times of moles of potassium hydroxide, and the resulting mixture was stirred for 1 hour and neutralized. The remaining water and unreacted HCl was then removed at 120℃ under 10 torr or less for 2 hours, and the resulting product was cooled to 40℃. Vinyldimethylchlorosilane was added thereto in an amount of 2 times of moles of silanol group, and the resulting mixture was then stirred and reacted for 6 hours to produce vinyldimethylsilyl-methylphenylpolysiloxane. 100g of vinyldimethylsilyl-methylphenylpolysiloxane prepared as such was added to a mixture of 100g of toluene and 200g of distilled water and stirred to conduct water washing. When the waste aqueous layer became neutral, one more water washing was conducted and then toluene was removed at 120℃ under 10 torr or less to obtain α,ω-vinyldimethylsilyl-methylphenylpolysiloxane having viscosity of 9800 cP at 25℃, solid content of 99.6% at 150℃ and refractive index of 1.53. The preparation process time and ion content were measured and shown in the following Table 1 (Example 1-1).
The same procedure was repeated one more to confirm the reproducibility. The preparation process time and ion content were measured and shown in the following Table 1 (Example 1-2).
Example 2
<Preparation of α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane>
According to the same method as explained in Example 1, α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane was prepared.
<Preparation of α-vinyldimethylsilyl-ω-trimethylsilyl-methylphenylpolysiloxane>
A flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane obtained above and purged with nitrogen for 30 minutes to make nitrogen atmosphere therein. The temperature in the flask was then elevated to 120℃ with continuous purging with nitrogen, and 10ppm (0.01g) of potassium hydroxide was added thereto. The viscosity was increased gradually as the reaction proceeded. At the viscosity of 16000 cP, hydrochloric acid was added in an amount of 1.5 times of moles of potassium hydroxide, and the resulting mixture was stirred for 1 hour and neutralized. The remaining water and unreacted HCl was then removed at 120℃ under 10 torr or less for 2 hours, and the resulting product was cooled to 40℃. Pre-mixed vinyldimethylchlorosilane in an amount of the same moles of silanol group and trimethylchlorosilane in an amount of the same moles of silanol group were added thereto, and the resulting mixture was then stirred and reacted for 6 hours to produce α-vinyldimethylsilyl-ω-trimethylsilyl-methylphenylpolysiloxane. 100g of α-vinyldimethylsilyl-ω-trimethylsilyl-methylphenylpolysiloxane prepared as such was added to a mixture of 100g of toluene and 200g of distilled water and stirred to conduct water washing. When the waste aqueous layer became neutral, one more water washing was conducted and then toluene was removed at 120℃ under 10 torr or less to obtain α-vinyldimethylsilyl-ω-trimethylsilyl-methylphenylpolysiloxane having viscosity of 8700 cP at 25℃, solid content of 99.5% at 150℃ and refractive index of 1.53. The preparation process time and ion content were measured and shown in the following Table 1.
Example 3
<Preparation of dimethylhydroxysilyl-(methylphenyl)(methylvinyl)copolysiloxane>
To a flask containing a mixture of 100g of toluene and 161.4g of water with stirring at 5℃ or less, a pre-mixture of 98g of methylphenyldichlorosilane and 2g of methylvinyldichlorosilane was added dropwise slowly so that the temperature in the flask might not exceed 30℃, and was hydrolyzed. Then, the resulting mixture was polymerized at 80℃ for additional 1 hour. The procedures thereafter were carried out in the same manner as in Example 1 to obtain dimethylhydroxysilyl-(methylphenyl)(methylvinyl)copolysiloxane having viscosity of 370 cP.
<Preparation of vinyldimethylsilyl-(methylphenyl)(methylvinyl)copolysiloxane>
A flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of dimethylhydroxysilyl-(methylphenyl)(methylvinyl)copolysiloxane obtained above and purged with nitrogen for 30 minutes to make nitrogen atmosphere therein. The procedures thereafter were carried out in the same manner as in <Preparation of α,ω-vinyldimethylsilyl-methylphenylpolysiloxane> of Example 1 to obtain vinyldimethylsilyl-(methylphenyl)(methylvinyl)copolysiloxane having viscosity of 9120 cP at 25℃, solid content of 99.6% at 150℃ and refractive index of 1.50. The preparation process time and ion content were measured and shown in the following Table 1.
Comparative Example 1
<Preparation of α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane>
According to the same method as explained in Example 1, α,ω-dimethylhydroxysilyl-methylphenylpolysiloxane was prepared.
<Preparation of α,ω-vinyldimethylsilyl-methylphenylpolysiloxane>
A flask equipped with condenser, receiver, thermometer, nitrogen feeding line and stirrer was charged with 100g of dimethylhydroxysilyl-methylphenylpolysiloxane obtained above, and purged with nitrogen for 30 minutes with heating to 40℃, to make nitrogen atmosphere therein. After sealing the flask, 1g of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane was added thereto and as a catalyst, trifluoromethanesulfonic acid was added in an amount corresponding to 1000ppm of reactants.
After completing the reaction, as a neutralizing agent, sodium bicarbonate was added in an amount corresponding to 2% of reactants to complete the neutralization. After filtering sodium bicarbonate, 100g of the reaction product was added to a mixture of 100g of toluene and 200g of distilled water and stirred to conduct water washing. When the waste aqueous layer became neutral, one more water washing was conducted and then toluene was removed at 120℃ under 10 torr or less to obtain α,ω-vinyldimethylsilyl-methylphenylpolysiloxane having viscosity of 8900 cP at 25℃, solid content of 99.5% at 150℃ and refractive index of 1.51. The preparation process time and ion content were measured and shown in the following Table 1 (Comparative Example 1-1).
The same procedure was repeated one more to confirm the reproducibility. The preparation process time and ion content were measured and shown in the following Table 1 (Comparative Example 1-2).
Table 1
Figure PCTKR2011001434-appb-T000001
In the above Table 1, “N.D.” means no detection, and “tr” means a tracing amount which was lower than 0.05ppm, the detection limit of ion content by the used ion analysis instrument.
In comparison Examples 1 to 3 with Comparative Example 1, Examples 1 to 3 according to the preparation process of the present invention showed 13.5 hours of the average preparation time, saving about 7.5 hours as compared with 21 hours for the prior art. In addition, the ion contents of the high refractive organopolysiloxanes prepared by the preparation process of the present invention were remarkably lower than those of the prior art. These results sufficiently satisfy the requirement of 5ppm or less which is the general standard of ion content for a silicone composition for light emitting diode.
According to the results as discussed above, the known method of prior art may reduce the ion content by employing an additional re-treatment procedure to control the ion content, but the preparation time further increases thereby.
<Evaluation of the properties of cured product>
100 parts by weight of the final product of each Example and Comparative Example was mixed with a methylphenylpolysiloxane so that H/Vi might become 2. A platinum catalyst was added thereto in an amount of 3ppm as platinum metal and mixed uniformly. The resulting mixture was exposed and cured at the temperature of 100℃ for 1 hour and then 150℃ for additional 1hour to obtain a colorless transparent sealing material.
The light transmission property, refractive index and hardness of the cured product of each Example and Comparative Example are compared below.
- Light transmission property
The sealing material was injected into 0.2mm space between two glass sheets and cured at 150℃ for 1 hour to prepare a cured silicone sample cell. The light transmission property of the cured silicone body was measured at 450nm wavelength and 25℃ by using an automatic spectrophotometer with visible light of arbitrary wavelength (400~700nm).
- Refractive index
The refractive index to a visible light (589nm) was measured at 25℃ by using an Abbe refractometer.
- Hardness
The sealing material was molded under pressure at 150℃ for 1 hour to form a sheet of the cured silicone body, and its hardness was measured according to JIS K6253 by using a hardness tester of A type or D type.
- Moisture permeability at high temperature
This property was evaluated at 85℃ with 85% of relative humidity.
Table 2
Figure PCTKR2011001434-appb-T000002
As can be seen from the above Table 2, all properties of the sealing materials obtained from the high refractive organopolysiloxanes prepared by Examples 1 to 3 according to the preparation method of the present invention were similar with those according to Comparative Example 1 corresponding to a prior art.

Claims (8)

  1. A method for preparing an organopolysiloxane, comprising the steps of:
    (1) conducting a condensation reaction of compounds of the following formula 1 by using an alkali condensation catalyst; and
    (2) conducting a condensation reaction of a compound of the following formula 2 with the product obtained in step (1) to prepare an organopolysiloxane of the following formula 3:
    Figure PCTKR2011001434-appb-I000005
    wherein
    each of R1, R2 and R4 is independently hydrogen; C1-C18alkyl; C5-C8cycloalkyl; C6-C10aryl; C6-C10arylC1-C6alkyl; C1-C6alkyl substituted with 1 to 3 halogens; or C2-C8alkenyl,
    R3 is C1-C6alkyl substituted with 1 to 3 halogens; halogen; or C1-C6alkoxy, and
    each of p, q and r is independently an integer of 0 to 1000.
  2. The method for preparing an organopolysiloxane according to claim 1, wherein as the alkali condensation catalyst, alkali metal hydroxide is used in an amount of 1~30ppm based on the total weight of reactants.
  3. The method for preparing an organopolysiloxane according to claim 1, wherein the condensation reaction of step (1) is conducted at 60℃ to 200℃ for 2 to 3 hours.
  4. A silicone composition comprising an organopolysiloxane prepared by the method according to claim 1.
  5. The silicone composition according to claim 4 which has a refractive index of 1.40 or higher to wavelength of 589nm at 25℃.
  6. The silicone composition according to claim 4 which provides a cured product having a durometer (Shore D) hardness of 30 or higher after curing at 150 ℃ for 1 hour.
  7. The silicone composition according to claim 6, wherein the cured product has a transmission ratio of 85% or more for visible light of 400 to 700nm.
  8. The silicone composition according to any one of claims 4 to 7 which is used for sealing a light emitting diode (LED) or for an optical lens.
PCT/KR2011/001434 2010-03-09 2011-03-02 A preparation method of silicone composition having high refractive index for light emitting diode device WO2011111945A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100021040A KR20110101791A (en) 2010-03-09 2010-03-09 A preparation method of silicon composition having high refractive index for light emitting diode device
KR10-2010-0021040 2010-03-09

Publications (2)

Publication Number Publication Date
WO2011111945A2 true WO2011111945A2 (en) 2011-09-15
WO2011111945A3 WO2011111945A3 (en) 2012-01-19

Family

ID=44573329

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/001434 WO2011111945A2 (en) 2010-03-09 2011-03-02 A preparation method of silicone composition having high refractive index for light emitting diode device

Country Status (2)

Country Link
KR (1) KR20110101791A (en)
WO (1) WO2011111945A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102757458A (en) * 2012-07-30 2012-10-31 嘉兴联合化学有限公司 Method and device for preparing tetramethyldihydrodisiloxane
CN103232600A (en) * 2013-05-23 2013-08-07 汕头市骏码凯撒有限公司 Method for preparing phenyl silicone resin with high-refractive index

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0148252B1 (en) * 1989-02-09 1998-08-17 . Process for preparing organosilicon compounds
KR20080110761A (en) * 2006-04-25 2008-12-19 에니콜로포브 인스티튜트 오브 신테틱 폴리머릭 머터리얼즈 (아이에스피엠) 오브 더 러시안 아카데미 오브 사이언스 Curable resin composition
JP2009203475A (en) * 2008-02-28 2009-09-10 Mitsubishi Chemicals Corp Sealing resin and method of producing the same
KR20090103785A (en) * 2008-03-27 2009-10-01 신에쓰 가가꾸 고교 가부시끼가이샤 Curable silicone rubber composition and optical semiconductor device using the same as sealing material
KR20100013368A (en) * 2008-07-31 2010-02-10 한국과학기술원 Siloxane resin for led encapsulation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0148252B1 (en) * 1989-02-09 1998-08-17 . Process for preparing organosilicon compounds
KR20080110761A (en) * 2006-04-25 2008-12-19 에니콜로포브 인스티튜트 오브 신테틱 폴리머릭 머터리얼즈 (아이에스피엠) 오브 더 러시안 아카데미 오브 사이언스 Curable resin composition
JP2009203475A (en) * 2008-02-28 2009-09-10 Mitsubishi Chemicals Corp Sealing resin and method of producing the same
KR20090103785A (en) * 2008-03-27 2009-10-01 신에쓰 가가꾸 고교 가부시끼가이샤 Curable silicone rubber composition and optical semiconductor device using the same as sealing material
KR20100013368A (en) * 2008-07-31 2010-02-10 한국과학기술원 Siloxane resin for led encapsulation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102757458A (en) * 2012-07-30 2012-10-31 嘉兴联合化学有限公司 Method and device for preparing tetramethyldihydrodisiloxane
CN102757458B (en) * 2012-07-30 2015-04-29 嘉兴联合化学有限公司 Method and device for preparing tetramethyldihydrodisiloxane
CN103232600A (en) * 2013-05-23 2013-08-07 汕头市骏码凯撒有限公司 Method for preparing phenyl silicone resin with high-refractive index
CN103232600B (en) * 2013-05-23 2015-01-28 汕头市骏码凯撒有限公司 Method for preparing phenyl silicone resin with high-refractive index

Also Published As

Publication number Publication date
KR20110101791A (en) 2011-09-16
WO2011111945A3 (en) 2012-01-19

Similar Documents

Publication Publication Date Title
CN102471585B (en) Silicon-containing curable composition and cured product thereof
EP1878768B1 (en) Curable silicone rubber compositions and cured product thereof
TWI402312B (en) An addition hardening type silicone resin composition for light emitting diodes
KR101206282B1 (en) Organopolysiloxane and curable silicone composition that contains aforementioned organopolysiloxane
US4988758A (en) Fluorosilicone rubber composition
US8168730B2 (en) Curable silicone rubber composition and cured product thereof
JP2005272697A (en) Curable silicone resin composition, sealing material for optical semiconductor and optical semiconductor device
KR20080031339A (en) Curable organopolysiloxane resin composition and optical part molded therefrom
WO2011090362A2 (en) Silicone resin
WO2012093907A2 (en) Curable composition
US9181400B2 (en) Silicone resin composition, cured silicone resin, and sealed optical semiconductor element
WO2014133287A1 (en) Resin composition for encapsulating optical element
WO2013115604A1 (en) Novel polyorganosiloxane, polycarbonate resin composition comprising same, and modified polycarbonate resin
KR20170098818A (en) Flame-retardant polyorganosiloxane composition, flame-retardant cured product, optical member, lens or cover for light source, and molding method
JP2009258385A (en) Curable silicone composition for optical lens
WO2012093910A2 (en) Curable composition
EP3266843B1 (en) Curable organosilicon resin composition
WO2012173460A2 (en) Curable composition
WO2012093909A2 (en) Curable composition
WO2011081326A2 (en) Light-transmitting resin for an encapsulating material and electronic device comprising same
WO2015060512A1 (en) Composition for sealing organic light emitting diode and organic light emitting diode display device manufactured using same
WO2011111945A2 (en) A preparation method of silicone composition having high refractive index for light emitting diode device
JP5036125B2 (en) Curable silicone resin composition
WO2012093908A2 (en) Curable composition
US4683320A (en) Novel organopolysiloxane, method for the preparation thereof and composition containing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11753550

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11753550

Country of ref document: EP

Kind code of ref document: A2