Classifications

• • 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
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing 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
  • C08G77/04—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
  • C08K5/56—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
  • 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
  • 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
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/476—Organic materials comprising silicon
• • 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
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • 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
  • C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/62—Nitrogen atoms
• • 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
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/852—Encapsulations
  • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins

Definitions

• the present invention relates to a thermosetting resin composition for encapsulating an optical device, and more particularly, polyhedral oligomeric silsesquioxane (POSS) and organic polysilazane (crosslinkable) to increase compatibility with the resin.
• the present invention relates to a resin composition for encapsulating an optical device, including a polysilazane) compound, having excellent mechanical properties and improved adhesion to a substrate and a barrier property against moisture or oxygen.
• Organic materials included in optical devices such as OLEDs and LCDs are very vulnerable to oxygen or water vapor in the air, and thus, when exposed to oxygen or water vapor, output reduction or premature performance degradation may occur. Accordingly, a method for extending the life of the device by protecting the devices using metal and glass has been developed, but metals generally have a disadvantage of lack of transparency and glass lack of flexibility.
• a flexible barrier film or encapsulant composition having flexibility has been developed for encapsulation of thin, light and flexible flexible OLEDs and other optical devices, and particularly silicone-based polymers having excellent light resistance and light transmittance. Compounds have been continuously preferred and developed as encapsulants in optical devices.
• silsesquioxane used is a powder type having a mixture of a ladder and a cage structure, and thus is a solvent-free process. It was unsuitable for most optical elements, especially LED encapsulation materials, which require a type.
• the present invention uses a modified silsesquioxane and organic polysilazane to increase the compatibility with the resin, can be manufactured in a solvent-free type and can reduce the outgas optical device encapsulation
• An object of the present invention is to provide a resin composition for sealing and an optical element sealing method using the same.
• the present invention to achieve the above object
• Each R is independently a compound of formula 3-1 or 3-2:
• R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms;
• Each Ra is independently hydrogen or chlorine
• z is an integer of 3 to 20, preferably an integer of 5 to 20 ;
• a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,
• M, Ma and Mb are each independently methyl or phenyl
• R X and R Y are each independently alkyl, alkenyl or aryl having 6 to 50 carbon atoms, preferably methyl, ethyl, vinyl or phenyl, more preferably R X is methyl, ethyl or Phenyl and R Y is methyl, ethyl or vinyl;
• n and n are each independently an integer of 1 to 20, wherein m + n is 2 to 21.
• the present invention provides a method for encapsulating an optical device using a sealing composition
• optical device encapsulation method using the optical device encapsulation composition.
• the present invention provides an optical element encapsulation film made of the optical element encapsulation composition.
• the resin composition for encapsulating the optical device of the present invention includes a polyhedral oligomeric silsesquioxane (POSS) having increased compatibility with the resin due to crosslinking, thereby improving solubility with the siloxane resin, thereby allowing a solvent-free process. Therefore, the encapsulation process characteristics are excellent, the crosslinking density is improved, and the mechanical characteristics are excellent.
• the resin composition of the present invention can be thermally cured by including an organic polysilazane compound and a modified polysilazane compound, and greatly reduces the outgas phenomenon by removing unreacted monomers that cause outgass through such a process. Since it can improve, a barrier characteristic can be improved significantly.
• the resin composition for encapsulating the optical element of the present invention can be used as a solvent-free process, and thus may be usefully used as an optical element, in particular, an LED encapsulation composition.
• the present invention can also be applied to a thick film encapsulation step.
• the resin composition for encapsulating the optical device of the present invention is characterized in that it comprises a polyhedral oligomeric silsesquioxane (POSS) and an organic polysilazane compound which can be crosslinked to increase compatibility with the resin.
• PES polyhedral oligomeric silsesquioxane
• organic polysilazane compound which can be crosslinked to increase compatibility with the resin.
• Cage-type polyhedral oligomeric silsesquioxanes commonly used in the art have a compatibility with the siloxane resins used as the main resin when used in the resin composition for encapsulation because the synthetic product thereof is in powder form. It is not good and it is not suitable for the resin composition for encapsulation, and since it melt
• composition of the present invention comprises a polyhedral oligomeric silsesquioxane of formula 1-1 or 1-2 in order to increase the compatibility with the siloxane resin:
• Each R is independently a compound of formula 3-1 or 3-2:
• R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms, preferably hydrogen, methyl, ethyl, vinyl or phenyl, and more preferably R 1 is Hydrogen or methyl, R 2 is methyl or phenyl, R 3 is hydrogen, methyl or phenyl, R 4 is hydrogen, methyl or vinyl, R 5 is methyl, vinyl or phenyl, R 6 is methyl, ethyl or methyl ego;
• Each Ra is independently hydrogen or chlorine
• z is an integer of 3 to 20, preferably an integer of 5 to 20 ;
• a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,
• M, Ma and Mb are each independently methyl or phenyl.
• the compound of Formula 1-1 or 1-2 is mainly based on the compound of Formula 3-1, the compound of Formula 3-2, the compound of Formula 3-3, or the following Formulas 3-4 and 3-5
• Compounds can be synthesized via condensation on distilled water with reactants:
• R 1 to R 6 , z, a and b are as defined above;
• Ra and R 7 are each independently hydrogen or chlorine
• x and y are each independently an integer of 1-100.
• the polyhedral oligomeric silsesquioxane usable in the present invention not only has sufficient compatibility with the siloxane resin even without dissolving in an organic solvent, but also includes a crosslinkable moiety, thereby improving the crosslinking density and mechanical properties of the resin composition. It can improve and also help to improve the gas barrier properties.
• the polyhedral oligomeric silsesquioxane may be used in an amount of 1 to 20% by weight based on the total composition, and when the content exceeds the content, compatibility with the siloxane resin may be reduced.
• composition of the present invention also comprises an organic polysilazane of formula (2) to remove outgas phenomena that lower barrier properties:
• R X and R Y are each independently alkyl, alkenyl or aryl having 6 to 50 carbon atoms, preferably methyl, ethyl, vinyl or phenyl, more preferably R X is methyl, ethyl or Phenyl and R Y is methyl, ethyl or vinyl;
• n and n are each independently an integer of 1 to 20, wherein m + n is 2 to 21.
• the organic polysilazane compound usable in the present invention is a compound which can be thermally cured, and when the vacuum / heat compounding process is applied to a resin composition for encapsulation containing the organic polysilazane compound, Outgassing can be improved by removing unreacted monomers. Therefore, when the composition of the present invention containing the organic polysilazane can be used to produce an encapsulation film having excellent surface properties, it can be applied to the encapsulation process of a thick film of several ⁇ m to several mm.
• the organic polysilazane compound may be used in an amount of 0.1 to 10% by weight based on the total composition.
• the organic polysilazane compound exceeds the content, the outgas phenomenon may be deepened and the barrier property may be reduced.
• composition of the present invention may further include a modified polysilazane compound of formula 4 to improve the barrier properties by improving the outgas phenomenon:
• Ra is alkyl of 1 to 20 carbon atoms or aryl of 6 to 50 carbon atoms
• Rb is a hydrocarbon of 1 to 20 carbon atoms, preferably a hydrocarbon of 1 to 5 carbon atoms;
• p is an integer from 1 to 15.
• the compound of Formula 4 may be synthesized through solution polymerization based on the compound of Formula 4-1 and the compound of Formula 4-3, or the compound of Formula 4-2 and compound of Formula 4-3 Can:
• R c is hydrogen or chlorine
• R d , R e and R f are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms.
• the modified polysilazane compound may be used in an amount of 0.1 to 15% by weight based on the total composition.
• the outgas phenomenon may be intensified to reduce barrier properties.
• the resin composition for encapsulating the optical device of the present invention may include a siloxane resin, a crosslinking resin, a silane coupling agent, and the like, which are commonly used in conventional amounts.
• the composition of the present invention may further include the modified polysilazane.
• the composition may further include a catalyst or a reaction retardant.
• the composition of the present invention is 1 to 20% by weight of the polyhedral oligomeric silsesquioxane, 0.1 to 10% by weight of the organic polysilazane, 30 to 85% by weight of the siloxane resin based on the total composition %, 5 to 40% by weight of crosslinked resin, and 0.05 to 10% by weight of silane coupling agent.
• the composition may comprise 0.1 to 15% by weight of the modified polysilazane siloxane resin, more preferably the composition may further comprise 1 to 3000 ppm of catalyst or 1 to 1000 ppm of reaction retardant. have.
• the siloxane resins usable in the present invention include polymethylvinyl siloxane, poly (methylphenyl) hydrosiloxane, poly (methylphenyl) siloxane, poly (phenylvinyl) -co- (methylvinyl) silsesquioxane, PDV-1635 from gelest, PMV-9925, PVV-3522, etc. are mentioned, As a crosslinking resin, a silsesquioxane copolymer, a phenylhydro silsesquioxane, or dimethyl silyl phenyl ether, etc. are mentioned, As a silane coupling agent, a methacrylate type
• Cyclosiloxane, etc., and the catalyst may be a platinum catalyst
• the reaction retardant may be ethynyl trimethyl silane or ethynyl triethyl silane and the like, but is not limited to these, each may include one or more.
• the present invention also provides an optical element encapsulation method using the optical element encapsulation composition and an optical element encapsulation film made of the optical element encapsulation composition.
• the optical element encapsulation method of the present invention is characterized by using the optical element encapsulation composition according to the present invention in a method of encapsulating the optical element with the optical element encapsulation composition. Processes applied to other encapsulation methods except for the use of the optical element encapsulation document may be well known processes.
• the present invention provides an optical element encapsulation film made of the optical element encapsulation composition
• the optical element encapsulation film of the present invention not only has excellent light transmittance and refractive index, but also has significantly improved hardness, adhesive strength and water vapor transmission rate,
• the optical element encapsulation film of the present invention When used as an encapsulation thin film of various optical elements is effective to extend the life of the optical element, in particular, it must be manufactured by a solvent-free process and can be used as the encapsulation film of LED that requires a thick film of several ⁇ m to several mm.
• Tetrasilanolphenyl POSS, dichloromethylpheylsilane, chlorodimethylvinylsilane were reactants, and the mixture was slowly added dropwise with distilled water at about 30 ° C. under normal pressure, followed by additional stirring at 50 ° C. for about 3 hours, and then the solvent was removed to remove the polyhedral oligomeric silses.
• Quioxane was synthesized.
• Octa Vinyl POSS and Hydrogenated poly (methylphenyl) siloxane Resin were synthesized by hydrosilylation reaction under platinum catalyst.
• Octa Hydro POSS and Vinyl terminated poly (methylphenyl) siloxane Resin were synthesized by hydrosilylation reaction under platinum catalyst.
• Siloxane Resin 1 Poly (methylphenyl) siloxane
• Siloxane resin 2 poly (phenylvinyl) -co- (methylvinyl) silsesquioxane
• Siloxane Resin 4 PVV-3522 (gelest)
• Crosslinked resin 2 dimethylsilylphenyl ether
• Organic polysilazane 1 HTT-1500 (AZ company)
• Organic polysilazane 2 Resin represented by the formula (2) HTT-1800 (AZ company)
• Modified polysilazane Modified polysilazane prepared in Synthesis Example 2
• Silane coupling agent Methacrylate-based cyclosiloxane
• Reaction Retardant 1 Ethynyltriethylsilane (gelest)
• Reaction Retardant 2 Ethynyltrimethylsilane (gelest)
• Light transmittance The composition is applied to the upper and lower glass and Teflon frame surface to have a size of 50 mm ⁇ 50 mm ⁇ 1 mm, then 1 hour at 150 °C, 1 hour at 170 °C
• the specimen was prepared by curing.
• the UV-vis spectrophotometer (Mecasys) was used to measure the transmittance of five points of the prepared specimen at a wavelength of 400 to 780 nm, and the light transmittance was evaluated from the average value within the obtained wavelength range.
• Hardness The composition was applied on a 20 mm ⁇ 20 mm ⁇ 15 mm mold, and then cured for 1 hour at 150 ° C. and 1 hour at 170 ° C. to prepare a specimen, and then measured using a hardness tester.
• Adhesive strength After applying the composition on a substrate of 100 mm ⁇ 15 mm, the two substrates were superimposed and cured for 1 hour at 150 °C, 1 hour at 170 °C to prepare a specimen, then a universal material tester ( Instron, product name: UTM-5566) was used.
• Refractive Index The composition was applied to the surface of a Teflon frame mold having a size of a rectangular parallelepiped (35 mm ⁇ 10 mm ⁇ 1 mm), and then cured for 1 hour at 150 ° C. and 1 hour at 170 ° C. to prepare a specimen. The resulting cured film was measured using an Abbe refractometer (589 nm).
• Examples 1 to 3 according to the present invention showed not only excellent light transmittance and refractive index, but also markedly improved hardness, adhesive strength and water vapor transmission rate.
• Examples 1 to 3 of the present invention showed excellent light transmittance and high reliability.
• C-POSS of Comparative Synthesis Examples 1 and 2 is a cage type (completely basket-shaped), and Products are light brown or yellowish-based. Therefore, the light transmittance is obtained in M-POSS of Synthesis Example 1 during curing after preparation of the final composition.
• the present invention is not suitable as the encapsulation material of the present invention in which the optical properties should be the basis, and the platinum catalyst used for synthesis may be added to the catalyst content of the whole composition and ultimately may adversely affect the reliability.
• the resin composition for encapsulating the optical device of the present invention includes a polyhedral oligomeric silsesquioxane (POSS) having increased compatibility with the resin due to crosslinking, thereby improving solubility with the siloxane resin, thereby allowing a solvent-free process. Therefore, the encapsulation process characteristics are excellent, the crosslinking density is improved, and the mechanical characteristics are excellent.
• the resin composition of the present invention can be thermally cured by including an organic polysilazane compound and a modified polysilazane compound, and greatly reduces the outgas phenomenon by removing unreacted monomers that cause outgas through such a process. Since it can improve, a barrier characteristic can be improved significantly.
• the resin composition for encapsulating the optical element of the present invention can be used as a solvent-free process, and thus may be usefully used as an optical element, in particular, an LED encapsulation composition. It can also be applied to the sealing process of a thick film of mm.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silicon Polymers (AREA)

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• 2013
  • 2013-02-28 KR KR1020130021845A patent/KR102016348B1/ko active Active
• 2014
  • 2014-02-24 JP JP2015560090A patent/JP6325006B2/ja active Active
  • 2014-02-24 WO PCT/KR2014/001458 patent/WO2014133287A1/ko not_active Ceased
  • 2014-02-24 US US14/769,155 patent/US9593241B2/en active Active
  • 2014-02-24 CN CN201480010669.7A patent/CN105008461B/zh active Active
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