WO2014084624A1 - Composition de silicium transparente durcissable pour dispositif optique - Google Patents

Composition de silicium transparente durcissable pour dispositif optique Download PDF

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WO2014084624A1
WO2014084624A1 PCT/KR2013/010899 KR2013010899W WO2014084624A1 WO 2014084624 A1 WO2014084624 A1 WO 2014084624A1 KR 2013010899 W KR2013010899 W KR 2013010899W WO 2014084624 A1 WO2014084624 A1 WO 2014084624A1
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group
carbon atoms
formula
compound
curable transparent
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PCT/KR2013/010899
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Korean (ko)
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이승아
최태근
박경남
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코오롱생명과학 주식회사
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Priority claimed from KR1020130142874A external-priority patent/KR20140070396A/ko
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Publication of WO2014084624A1 publication Critical patent/WO2014084624A1/fr

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • Curable transparent silicone composition for optical devices Name of invention: Curable transparent silicone composition for optical devices
  • the present invention relates to a curable transparent silicone composition for an optical device.
  • Japanese Patent Laid-Open Publication No. 2004-186168 and Japanese Patent Laid-Open Publication No. 2006-202952 disclose addition-curable silicone resin compositions cured by hydrosilylation reactions between silicon atom-bonded alkenyl groups and hydrogen atoms bonded to silicon atoms.
  • Japanese Patent Application Laid-Open No. 2006-342200 discloses an addition-curable silicone resin composition in which the organic polysiloxane has a silicon atom-bonded alkenyl group, and has a waxy form at 23 ° C.
  • a linear organic polysiloxane having a viscosity of lOOOOmPa-s or less a silicone resin composition for die bonding having high hardness and excellent heat resistance, transparency, and light transmittance in a low wavelength region using a high chain three-dimensional network organopolysiloxane resin
  • Japanese Patent Laid-Open No. 2008-031190 discloses Inorganic resin is contained in the curable silicone composition containing an addition-curable silicone resin.
  • a method of suppressing the occurrence of corrosion by sulfidation of a metal member using a silver exchanger is disclosed.
  • an organic polysiloxane including an alkenyl group bonded to a silicon atom used as a base resin is first cured at a low silver of 70 to 100 ° C. and then subjected to first curing to form a chain.
  • the secondary reactive side chain part reacts to form secondary crosslinking at high temperature of 150 ° C or higher.
  • the crosslinking is formed in such a way that heavy structure hangs on the light structure during rapid high hardening. There is a problem that the residual internal stress is increased and the physical properties are lowered.
  • Japanese Patent Laid-Open No. 2005-005614 has two or more epoxy groups in one molecule, including silicon compounds having an molecular weight of 500 to 2,100 or less, acid anhydride, and a catalyst.
  • a low-pressure thermosetting resin composition is disclosed, and Japanese Patent Laid-Open No. 2006-077234 contains an organopolysiloxane having a specific structure having a polystyrene equivalent weight average molecular weight of 5xl0 3 g / mol or more, and a condensation catalyst.
  • the resin composition for LED element encapsulation which improves heat resistance, ultraviolet-ray resistance, optical transparency, toughness, and adhesiveness is disclosed.
  • U.S. Patent Publication No. 2007—0298223 discloses curing in the presence of a thermally activated organoborane amine complex, or free radically polymerizable organosilicon monomers, oligomeric or polymers, and organoborane amine complexes and amine groups.
  • a curable composition containing a free radically polymerizable organosilicon monomer, an oligomer or a polymer that is cured by blending a male compound in an oxygen-containing environment is disclosed, and WO2007 / 100445 discloses an alkenyl action.
  • Polyphenyl-containing polyorganosiloxanes Si-H functional phenyl-containing polyorgano-siloxanes, or combinations thereof;
  • hydrosilylation-curable compositions, including hydrosilylation catalysts which can improve the reliability in light emitting device applications by forming silicone products having optical transparency, high refraction, resistance to high temperatures and high mechanical strength upon curing. Is disclosed.
  • U.S. Patent No. 5,982,041 also discloses free radical reaction of acrylic functional organopolysiloxane induced by exposure to high energy radiation, and hydrogen functional organo-silicon-bonded with alkenyl functional organopolysiloxane.
  • a siloxane composition for a silicone die attach adhesive is disclosed that is cured through hydrosilylation reaction with nopoly siloxane.
  • Korean Patent No. 377590 discloses (a) an organopolysiloxane containing at least two alkoxy groups bonded to silicon atoms in each molecule and not containing an alkenyl group bonded to silicon atoms, and two bonded to silicon atoms in each molecule.
  • Organopolysiloxanes each containing three or more alkoxy groups and two alkenyl groups bonded to silicon atoms; Organopolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in each molecule; Condensation reaction catalyst; And a curable silicone composition useful for light emitting diode display devices by forming a cured product having excellent matte properties upon curing by hydrosilylation reaction and condensation reaction, including an air-oxidation-curable unsaturated compound, together with a platinum catalyst.
  • US Patent Publication No. 2008-0185601 discloses an organopolysiloxane resin containing an alkenyl group and a phenyl group and having a weight average molecular weight of 3000 or more as measured by gel chromatography using polystyrene as a reference; Organooligosiloxanes including alkenyl groups and phenyl groups; Organohydrogen siloxane or organohydrogenpolysiloxane of a specific structure; Addition semicoagulant catalyst; And an addition-curable organopolysiloxane resin capable of forming a product, including a releasing agent, having a degree of cure of 60 to 100 at 25 ° C. and a degree of cure of 40 to 10 CASTM D2240-86 at 150 ° C.).
  • the composition is disclosed.
  • WO 2006/077667 discloses a vinyl group-containing organopolysiloxane having a three-dimensional network structure of a specific structure; Organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule; And hydrosilylation including banung catalyst, a curing after 10 ⁇ _6 290xl0 rc linear expansion coefficient of the light-emitting element-sealing silicone composition capable of forming a cured product having the disclosed.
  • Korean Patent No. 704883 discloses an LED encapsulation composition including at least one polyorganosiloxane and an additional semi-heung catalyst, which becomes a resinous material upon curing.
  • An object of the present invention is to shorten the curing time, high shear modulus at high temperature, high crosslinking degree, adhesion strength, surface curing degree and transparency, and can maintain transparency without fear of discoloration even after long-term exposure to ultraviolet light, moisture and heat.
  • Curable transparent for optical devices useful as adhesives or transparent materials for optical semiconductors It is to provide a silicone composition.
  • an organic silicone compound a crosslinking agent, and an addition group
  • a bonding structure selected from the group consisting of, and containing at least three alkenyl groups having 2 to 10 carbon atoms bonded directly to the silicon atom (Si) in the molecule or bonded to Si through the oxygen atom (0),
  • a curable transparent silicone composition for an optical device comprising an organosiloxane compound having a branched or three-dimensional network structure having an intramolecular vinyl content of 0.1 to 20 mmole / g.
  • the organosilicon compound is selected from the group consisting of a first organic silicon compound of (a-1), a second organic siloxane compound of (a-2), and a mixture thereof It may be chosen:
  • (a-1) a first organosilicon compound selected from the group consisting of compounds of the formula la to lc;
  • a second organic siloxane compound of formula (4) comprising three or more alkenyl groups directly bonded to:
  • a, b and c are integers, respectively, 0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 3, and 0 ⁇ c ⁇ 3.
  • R ' is an alkenyl group having 2 to 10 carbon atoms
  • RCRII RCRII (wherein each R is independently an aliphatic saturated hydrocarbon group of 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group of 2 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 30 carbon atoms, hydroxy group, 1 carbon atom)
  • Y and Z are each independently aliphatic saturation having 1 to 20 carbon atoms
  • Hydrocarbon group aliphatic unsaturated hydrocarbon group of 2 to 20 carbon atoms, aromatic hydrocarbon group of 6 to 30 carbon atoms, hydroxy group, epoxy group, amino group (-NR a R b , wherein R a and R b are each independently of 1 to 5 and It is selected from the group consisting of functional groups of the formula (2):
  • e, f, and g are integers, respectively, 0 ⁇ e ⁇ 100, l ⁇ f ⁇ 5, 0 ⁇ g ⁇ 2, the generation number when expressed as a dendrimer structure is 2 or less,
  • R is each independently an aliphatic saturated hydrocarbon group of 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group of 2 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxy group, an alkoxy group of 1 to 20 carbon atoms, an epoxy group, an amino group ( -NR a R b , wherein R a and R b are each independently an alkyl group having 1 to 5 carbon atoms) and combinations thereof, and
  • T is * " ( 0 ) l R (wherein R 'is an alkenyl group having 2 to 10 carbon atoms, ⁇ is an integer of 0 or 1),
  • R and ⁇ are selected so that the number of alkenyl groups having 2 to 10 carbon atoms in the compound molecule of formula lb is 3 or more
  • h, i and j are each an integer of 0 h ⁇ 100, l ⁇ i ⁇ 5, 0 ⁇ j ⁇ 2,
  • R is each independently an aliphatic saturated hydrocarbon group of 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group of 2 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxy group, an alkoxy group of 1 to 20 carbon atoms, an epoxy group, an amino group (-NR a R b , wherein R a and R b are each independently an alkyl group having 1 to 5 carbon atoms) and a combination thereof; and T is ' ⁇ (wherein R' is an alkenyl group having 2 to 10 carbon atoms, ⁇ is an integer of 0 or 1),
  • R and ⁇ are selected so that the number of alkenyl groups having 2 to 10 carbon atoms in the compound molecule of formula lc is 3 or more
  • a, b, c, d and e are integers, respectively, l ⁇ a ⁇ 30, l ⁇ b ⁇ 20, 0 ⁇ c ⁇ 30, 0 ⁇ d ⁇ 10 and l ⁇ e ⁇ 30, and
  • R is each independently an aliphatic saturated hydrocarbon group of 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group of 2 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxy group, an alkoxy group of 1 to 20 carbon atoms, an epoxy group, an amino group ( NR a R b , wherein R a and R b are each independently an alkyl group having 1 to 5 carbon atoms) and a combination thereof, provided that at least three of R are alkenes having 2 to 10 carbon atoms; Neil)
  • the first organosilicon compound is represented by the formulas 3a to 3c
  • the second organic siloxane compound is a Q-unit (Si0 4/2 ) in a molecule. , or Q- unit and T- unit (Si0 3/2) containing 3 to 30 minutes, a ground repeating units (branched unit), and a terminal unit (terminal unit) -Si containing! ⁇ I ⁇ R ⁇ wherein , R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, R 3 is an alkenyl group having 2 to 10 carbon atoms) may be an organic siloxane compound of a three-dimensional network structure.
  • the second organic siloxane compound may be selected from the group consisting of compounds represented by the following Chemical Formulas 6a to 6c:
  • n is an integer of 2 to 30
  • the second organic siloxane compound may have a viscosity at 25 ° C. of 100 mPa-s or more in liquid or solid form.
  • the crosslinking agent may be a third organic siloxane compound including a repeating unit represented by the following Chemical Formula 7, and including two or more hydrogen atoms in one molecule bonded to silicon atoms:
  • p and q are integers 0 ⁇ p ⁇ 4, 0 ⁇ q ⁇ 4 and 0 ⁇ p + q ⁇ 4, and
  • Each R 1 is independently an aliphatic saturation having 1 to 20 carbon atoms, unsubstituted or substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen group, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and a cyano group Hydrocarbon group, aromatic hydrocarbon group having 6 to 30 carbon atoms, and combinations thereof.
  • crosslinking agent may be selected from the group consisting of compounds of the formula 8a to 8d:
  • Each R 1 is independently an aliphatic saturation having 1 to 20 carbon atoms, unsubstituted or substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen group, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and a cyano group A hydrocarbon group, an aromatic hydrocarbon group of 6 to 30 carbon atoms, and a combination thereof;
  • V is an integer from 1 to 20
  • w is an integer from 1 to 10
  • X is an integer from 0 to 100
  • y is an integer from 1 to 50.
  • the crosslinking agent may have a viscosity at 25 ° C. of less than l, 000 mPa-s.
  • the crosslinking agent may be included in an amount such that the hydrogen atom bonded to the silicon atom in the crosslinking agent molecule becomes 0.5 to 3 times molar with respect to the alkenyl group bonded to all the silicon atoms in the organosilicon compound.
  • the crosslinking agent may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the organosilicon compound.
  • the addition semi-heunggung catalyst may be a platinum group metal catalyst.
  • the addition reaction catalyst may be included in an amount of 10 to 5000 ppm in terms of mass of the platinum group metal element based on the total weight of the organic silicon compound.
  • the curable transparent silicone composition for an optical device may have a light transmittance of 90% or more at 450 nm and 600 nm compared to glass light transmittance when cured after coating with a thickness of 1 mm to 2 mm on glass.
  • the shear modulus when curing the curable transparent silicone composition for optical devices to a thickness of 2mm is less than 150Mpa at 25 ° C, 100 ° C or more
  • the temperature may be at least 20 Mpa.
  • the adhesive transparent composition for an optical device uses a organosilicon compound in a regular, highly branched form as a main material and undergoes a crosslinking reaction without aromaticity through a highly reactive terminal crosslinking agent, and thus has a short curing time and high temperature. It has high shear modulus, high crosslinking strength, adhesive strength, surface hardening degree and transparency at, and it is useful as an optical semiconductor adhesive or transparent material because it can maintain transparency without fear of discoloration even after long-term exposure to ultraviolet rays, moisture and heat. .
  • FIGS. 1 to 5 are graphs showing the results of Fourier Transform Infrared Spectroscopy (FT-IR) observations on the compounds of Synthesis Examples 1 to 5, respectively.
  • Figure 6 is a graph showing the results of observing the point of curing completion at a fixed temperature (150 ° C) for the curable transparent silicone composition for optical devices of Examples 1 to 21 and Comparative Examples 1,2.
  • FT-IR Fourier Transform Infrared Spectroscopy
  • Fig. 7 is a graph showing the results of measuring the light transmittance after curing the water after curing the water-curable transparent silicone composition of Examples 1 to 21 and Comparative Examples 1 and 2.
  • 'substituted' means that a hydrogen is a halogen group, a hydroxyl group, a carboxy group, a cyano group, a nitro group, an amino group, a thio group, a methyl thi group, an alkoxy group aldehyde group, an epoxy group, an ether group, an ester group, a carbonyl group , Any one selected from the group consisting of acetal groups, ketone groups, alkyl groups, perfluoroalkyl groups, cycloalkyl groups, heterocycloalkyl groups, allyl groups, benzyl groups, aryl groups, heteroaryl groups, derivatives thereof, and combinations thereof Means replaced do.
  • the present invention relates to a process for preparing a curable transparent silicone composition for an optical device using (a) an organosilicon compound, (b) a crosslinking agent, and (c) an addition reaction catalyst, wherein - prior art including the atom to form a cross-linking reaction to at least by for the three or more cross-linkable regularity organic silicon compound of high branching form with conventional silicon compound of the terminal and side chain portion ⁇ ] I reaction site, and In contrast, cure time is short because crosslinking reaction proceeds without directivity, and it shows high shear modulus, high crosslinking degree, adhesive stress, surface hardening degree and transparency at high temperature, and discoloration after long-term exposure to ultraviolet ray, moisture and heat. can maintain transparency in the semiconductor light C without adhesive also is characterized in that it is useful as a transparent material.
  • the organosilicon compound of component (a) is contained within a unit molecule
  • a bonding structure selected from the group consisting of, containing at least three alkenyl groups having 2 to 10 carbon atoms bonded directly to Si in the molecule or bonded to Si through an oxygen atom (0), vinyl in the molecule It may be a branched or three-dimensional organosiloxane compound having a content of 0.1 to 20 mmole / g, preferably 0.5 to 12 mmole / g.
  • the vinyl content is less than 0.1 mmol / g, the crosslinking degree is lowered in the composition, thereby reducing shear modulus and adhesive strength.
  • the vinyl content is greater than 20 mmol / g, the vinyl content may be easily broken after curing in the composition or yellowed easily by heat. .
  • the organosilicon compound of component (a) may have a dendrimer structure as an example of a branched chain or three-dimensional network structure, in which case it may be preferable that the number of generations is three or less. If the number of generations exceeds 3, it may be difficult to control the crosslinking reaction and curing rate, and it may be difficult to commercialize due to the increase of the synthesis step.
  • the organosilicon compound of the component (a) may be selected from the group consisting of the first organosilicon compound of the following (al), the second organic siloxane compound of the following (a-2), and a mixture thereof. have:
  • the first organosilicon compound comprises a branched or three-dimensional, alkenyl group having 2 to 10 carbon atoms, more preferably 3 or more vinyl groups, directly bonded to Si in the molecule or bonded to Si via an oxygen atom (0). It may be a polysiloxane compound or a polycarbosiloxane compound of a network structure. More specifically, it may be selected from the group consisting of compounds of the formula la to lc:
  • R is independently an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms including a t-butyl group or the like) or a cycloalkyl group having 3 to 20 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclonuclear group, etc.); Alkenyl group (e.g., ethenyl group, propenyl group, butenyl group, etc.), alkynyl group (e.g., ethynyl group, propynyl group, butynyl group, etc.) having 2 to 10 carbon atoms, or cycloalkyl having 3 to 20 carbon atoms C2-C20 aliphatic unsaturated hydro
  • Y and Z are each independently an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, etc.), or 3 to 20 carbon atoms C1-C20 aliphatic saturated hydrocarbon group containing a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group, a cyclonuclear group, etc.); Alkenyl groups having 2 to 10 carbon atoms (eg, ethenyl group, propenyl group, butenyl group, etc.), alkynyl groups having 2 to 10 carbon atoms (eg, ethynyl group, propynyl group, butynyl group, etc.), or 3 carbon atoms C2-C20 aliphatic unsaturated hydrocarbon group containing a cycloalken
  • e, f and g are each an integer of 0 ⁇ e ⁇ 100, l ⁇ f ⁇ 5, 0 ⁇ g ⁇ 2, and
  • Each R independently represents an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc.), or Aliphatic saturated hydrocarbon groups having 1 to 20 carbon atoms including a cycloalkyl group having 3 to 20 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclonuclear group, etc.); Alkenyl groups having 2 to 10 carbon atoms (eg, ethenyl group, propenyl group, butenyl group, etc.), alkynyl groups having 2 to 10 carbon atoms (eg, ethynyl group, propynyl group, butynyl group, etc.), or 3 carbon atoms Aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms, including cycloalkenyl groups of 20 to 20; C6-C30 aromatic hydro
  • R and ⁇ may be selected such that the alkenyl group having 2 to 10 carbon atoms, preferably the number of vinyl groups in the compound molecule of Formula lc is three or more.
  • R and ⁇ may be selected such that the alkenyl group having 2 to 10 carbon atoms, preferably the number of vinyl groups in the compound molecule of Formula lc is three or more.
  • h, i and j are each integers 0 ⁇ h ⁇ 100, l ⁇ i ⁇ 5, 0 ⁇ j ⁇ 2, and
  • R and T are as defined in formula lb above.
  • the first organosilicon compound of the component (a-1) may have a dendrimer structure, in which case it may be preferable that the generation number is 2 or less. If the number of generations is greater than 2, the viscosity may be high and control of the composition may be difficult, and the synthesis step may be increased, making commercialization difficult.
  • the first organosilicon compound of component (a-1) may be a compound of formulas 3a to 3c:
  • the dotted line represents a dendrimer structure.
  • the second organic siloxane compound includes silicon (Si) in a unit molecule, and a Q- oil (quardri— function functional siloxane group: Si element having four —O— (siloxane bonds) bonded thereto, or a Q-unit and T It contains a complex structure of a unit (Tri-functional siloxane group: Si element bonded to three (siloxane bond)), alkenyl group having 2 to 10 carbon atoms directly bonded to Si in the molecule, preferably vinyl group
  • an organosiloxane compound containing two or more specifically, it may have a structure of the following general formula (4):
  • a, b, c, d and e are integers, respectively, l ⁇ a ⁇ 30, l ⁇ b ⁇ 20, 0 ⁇ c ⁇ 30, 0 ⁇ d ⁇ 10 and l ⁇ e ⁇ 30,
  • Each R independently represents an alkyl group having 1 to 20 carbon atoms (eg, methyl group ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, etc.), or a cycloalkyl group having 3 to 20 carbon atoms (eg For example, C1-C20 aliphatic saturated hydrocarbon group containing a cyclopropyl group, a cyclobutyl group, a cyclonuclear group etc .; Alkenyl groups having 2 to 10 carbon atoms (eg, ethenyl group, propenyl group, butenyl group, etc.), alkynyl groups having 2 to 10 carbon atoms (eg, ethynyl group, propynyl group, butynyl group, etc.), or 3 carbon atoms Aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms, including cycloalkenyl
  • the second organic siloxane compound may be a Q unit (Si0 4/2 ), or a Q-unit and a T— as a branched repeating unit in a molecule, as shown in Formula 5 below.
  • 3 to 30 unit species preferably 3 to 10 units, and -SiR 1 ! ⁇ 2 ! ⁇ as a terminal unit
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms
  • R 3 may be an organosiloxane compound having a three-dimensional network structure containing an alkenyl group having 2 to 10 carbon atoms, preferably a vinyl group.
  • the second organic siloxane compound may be selected from the group consisting of compounds represented by the following Chemical Formulas 6a to 6c.
  • 1 may be an integer of 1 to 30, preferably an integer of 1 to ⁇ 10)
  • n may be an integer of 2 to 30
  • the second organic siloxane compound having the above structure also has a viscosity of 100 mPa at 25 ° C. It may be desirable to have a liquid or solid phase of at least s. Since it has such a viscosity characteristic, it can exhibit a viscosity adjustment effect according to the content of the second organic siloxane compound.
  • the chain has priority.
  • reaction can proceed without aromaticity through a semi-ungung terminal crosslinking agent, that is, an H-terminated organosiloxane terminated with hydrogen atoms, so that curing time is short and crosslinking degree is high.
  • the shear modulus, adhesive stress, surface hardness, and transparency at high temperatures are improved, and transparency can be maintained without fear of discoloration even after exposure to ultraviolet rays, moisture, and heat for a long time.
  • the first and second organic siloxane compounds having a crosslinking point formed with a short crosslinking agent shrinkage may be minimized even at high temperature curing.
  • the first organic silicon compound and the second organic siloxane compound may be included alone or in combination in the curable transparent silicone composition for the optical device. Compared to the single use, the reaction rate improvement effect by the first organic silicone compound and the physical property by the second organic siloxane compound can be simultaneously exhibited.
  • the mixing ratio is not particularly limited, but the first organosilicon compound and the second organic siloxane compound are included in a weight ratio of 1: 4 to 1: 8 in terms of improvement of the effect of the present invention. It is preferable to be, more preferably may be included in a weight ratio of 1 : 4 to 1 : 5 . If the mixing ratio is less than 1: 4, the composition may be slightly yellowish and yellow easily with heat. If the ratio exceeds 1: 8, the effect of the system 1 organosilicon compound may be insignificant.
  • Curable transparent silicone composition for an optical device according to the present invention is the component
  • the crosslinking agent is included as a component (b) which serves to harden a composition by inducing crosslinking by the alkenyl group and hydrosilylation reaction in the organosilicon compound of (a).
  • the crosslinking agent may be used in a transparent silicone composition for curing for optical devices, but may include two or more hydrogen atoms bonded to silicon atoms in one molecule to dilute not only the crosslinking agent, but also the transparent silicone composition.
  • Preference may be given to third organic siloxane compounds which can also act as semi-aqueous diluents to achieve a suitable viscosity.
  • the third organic siloxane compound is represented by the formula
  • It contains a repeating unit, containing two or more hydrogen atoms (ie, SiH groups) bonded to the silicon atoms in one molecule, preferably 2 to 50
  • Organohydrogenpolysiloxane can be:
  • R 1 each independently represent a substituted or unsubstituted aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms;
  • R When R is substituted, it may be substituted with a functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen group, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and a cyano group.
  • R 1 is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, nuclear group, heptyl group, octyl group, nonyl group, decyl group
  • Alkyl groups such as; Cycloalkyl groups such as cyclonuclear group; Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; Aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; Some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine atom, fluorine atom and bromine atom,
  • Halogenated alkyl groups such as chloromethyl group, 3—chloropropyl group and 3, 3, 3-trifluoropropyl group; Or a cyanoethyl group substituted with a cyano group, and among these, an alkyl group having 1 to 10 carbon atoms may be preferable, and a methyl group may be more preferable because of excellent improvement in light resistance and heat resistance of the cured product. have.
  • the organohydrogenpolysiloxane of the general formula (7) at least 0.01 mol% or more of the total R 1 is a methyl group has excellent compatibility with the components (a) to (c), the turbidity or phase separation of the composition No concern
  • 0.05 to 10 mol% may be a methyl group.
  • p and q are integers 0 ⁇ p ⁇ 4, 0 ⁇ q ⁇ 4 and 0 ⁇ p + q ⁇ 4, preferably 0 ⁇ p ⁇ 3, l ⁇ q ⁇ 3 and l ⁇ p + q ⁇ 3.
  • the hydrogen atom (i.e., SiH group) bonded to the silicon atom to be contained may be located at either the molecular chain terminal or the middle of the molecular chain, or both.
  • the molecular structure of the third organic siloxane compound may be any one of linear, cyclic, branched and three-dimensional network structure, the number (or degree of polymerization) of silicon atoms in one molecule is 1 to 500, preferably Is preferably 3 to 200.
  • the content of the hydrogen atom bonded to the silicon atom is preferably in the range of 0.1 to 20 mmole / g per lg of the third organic siloxane compound, and 1 to 10 mmole / g. It is more preferable that it is a range.
  • the third organic siloxane compound is l, 000 mPa at 25 ° C. s or less , More preferably, having a viscosity of 10 to 100 mPa ⁇ s can obtain the effect of viscosity reduction.
  • the third organic siloxane compound examples include 1,1,3,3-tetramethyldisiloxane 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrocyclocyclopolysiloxane, methylhydrogensiloxane and dimethylsiloxane Cyclic copolymer, both ends
  • Methylhydrogensiloxane diphenylsiloxane copolymer both ends
  • R 1 is the same as defined in Formula 7, ⁇ is an integer of 1 to 20, w is an integer of 1 to 100, X is an integer of ⁇ to 100, and y is of 1 to 50 Is an integer.
  • One of these third organic siloxane compounds may be used alone, or two or more thereof may be mixed and used.
  • the component (b) is an amount such that the hydrogen atom bonded to the silicon atom in the component (b) is 0.5 to 3 times molar relative to the entire silicon atom or the alkenyl group bonded to the silicon atom through oxygen in the organosilicon compound of the component (a). It is preferably included as. When included in such a content it can exhibit a better improvement effect.
  • component (b) is preferably included 1 to 15 parts by weight based on 100 parts by weight of the organosilicon compound of component (a).
  • component (c) is preferably included 1 to 15 parts by weight based on 100 parts by weight of the organosilicon compound of component (a).
  • the curable transparent silicone composition for an optical device according to the present invention also has an alkenyl group of component (a) and a SiH group in a crosslinking agent of component (b).
  • a hydrosilylation reaction catalyst ie, an addition reaction catalyst, may be included.
  • a platinum group metal catalyst may be used as the addition semi-heung catalyst, and specific examples thereof include platinum group metals such as platinum, palladium and rhodium; Chloroplatinic acid; Alcohol-modified chloroplatinic acid, such as a counter-product of chloroplatinic acid and monohydric alcohol; Platinum group-containing coordination compounds of chloroplatinic acid with ellepins, vinylsiloxane or acetylene compounds; Tetrakis (triphenylphosphine) palmation and
  • Platinum group metal compounds such as chlorotris (triphenylphosphine) rhodium and the like.
  • Chloride that can be used alone or in combination of two or more of the above-described addition reaction catalysts, which has good compatibility with the components (a) and (b) and contains little chlorine impurities. It may be desirable to modify the platinum acid to silicon.
  • the addition reaction catalyst may be included in the curable transparent silica composition for optical devices as an effective amount as a catalyst, preferably 10 to 5000ppm in terms of mass of the platinum group metal element relative to the total weight of the organosilicon compound of the component (a). It may be included as, the hydrosilylation reaction is included in the content of 50 to 2000ppm
  • the curable transparent silicone composition for an optical device comprises an alkenyl group or a hydroxyl group bonded to two or more silicon atoms in a unit molecule together with the component (a), and is bonded by hydrogen bonding with an adherend while reducing the viscosity.
  • It may include a siloxane compound for viscosity adjustment.
  • the viscosity-adjusting siloxane compound includes a repeating diorganosiloxane unit whose main chain is represented by the following formula (9), and both ends of the molecular chain are triorganosiloxy groups (R 3 Si 1/2). It may be a linear, branched or three-dimensional network of diorganopolysiloxanes, which are blocked with)) and contain at least two alkenyl or hydroxy groups bound to silicon atoms in a unit molecule:
  • R 1 and R 2 are each independently an alkenyl group having 2 to 20 carbon atoms, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 30 carbon atoms. Is selected.
  • the viscosity-adjusting siloxane compound is silicon in a unit molecule It may contain 2 to 10, more preferably 2 to 5 alkenyl or hydroxy groups bonded to the atom.
  • the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms.
  • Specific examples thereof include vinyl group, allyl group, isopropenyl group : butenyl group, pentenyl group, nucleenyl group and the like, and most preferably vinyl group.
  • the alkenyl group or hydroxy group may be present at any one of the molecular chain terminal and the molecular chain non-terminal (that is, the molecular chain side chain) in the molecule, or both may be present, at least at both ends of the molecular chain. Do.
  • the alkenyl group or hydroxy group is preferably included in 0.01 to 5.00mmole / g, preferably 0.10 to 0.50mmole / g of all organic groups. If the content of the alkenyl group or hydroxyl group is less than 0.01mmole / g, the degree of crosslinking is poor and the adhesive strength is not preferable.
  • the viscosity-adjusting siloxane compound may be selected from the group consisting of compounds of Formulas 10a to 10g:
  • R 3 and R 4 are each independently selected from the group consisting of an alkenyl group having 2 to 20 carbon atoms, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 30 carbon atoms, and f is 0 to 200, preferably an integer of 3 to 120, g is an integer of 1 to 10, preferably 1 to 5, h is 0 to 200, preferably of 3 to 110
  • the siloxane compound for viscosity adjustment mentioned above can be used individually by 1 type, or can mix and use 2 or more types.
  • the viscosity-adjusting siloxane compound may be contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the organosilicon compound of component (a), so that a preferable viscosity reduction effect may be obtained without fear of deterioration of physical properties, and preferably 10 to 20 parts by weight. May be included.
  • It may include a silane compound containing at least one alkoxy group which performs adhesion promoting action by hydrogen bonding with the adherend.
  • the silane compound may be a compound of Formula 11
  • R 6 and R 7 are each independently aliphatic having 1 to 8 carbon atoms
  • R 8 is selected from the group consisting of vinyl group, glycidyl group, styryl group, methacryl group, acryl group, ureido group chloroalkyl group, mercapto group, isocyanate group, amino group, dimethylamino group, imidazole group, acetoacetate group and epoxy group A hydrocarbon group having 1 to 8 carbon atoms substituted with a selected functional group, and
  • z and z ' are integers of 1 ⁇ ⁇ 4, 0 ⁇ ' ⁇ 3 and 1 ⁇ + ⁇ ' ⁇ 4.
  • the silane compound may be triethyl silicate
  • silane compound is an organosilicon compound of the component (a)
  • the curable transparent silicone composition for an optical device may optionally include a thixotropic control agent such as silica article; Light scattering agents such as crystalline silica; Reinforcing materials such as silica and fumed silica; Phosphor; Viscosity modifiers such as petroleum solvents and non-reactive silicone oils having no semi-functional functional groups; (A) having at least one of alkenyl groups such as carbon-functional silanes, epoxy groups, alkoxy groups, hydrogen atoms bonded to silicon atoms (i.e., SiH groups) and vinyl groups bonded to silicon atoms; Adhesion improvers such as silicone compounds other than components; Conductivity imparting agent containing metal powders, such as silver and gold: Inorganic pigments, such as cobalt blue; Coloring agents such as organic dyes; Heat resistance and flame retardant improvers such as cerium oxide, zinc carbonate, manganese carbonate, iron oxide, titanium oxide, carbon black and the like; 3-methyl-1
  • Reaction inhibitors such as benzotriazole, phosphine compound and mercapto compound; Or an additive such as a wavelength regulator.
  • the additive may be used in an appropriate amount depending on the use within the scope that does not impair the effects of the present invention.
  • Curable transparent silicone composition for an optical device according to the present invention having the composition as described above, 80 mol% or more, preferably 90 to 100 mol% of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups in the composition
  • the methyl group is more preferable because it is excellent in heat resistance and light resistance (ultraviolet resistance) and excellent in resistance to deterioration including discoloration due to stress such as heat and ultraviolet rays.
  • the curable transparent silicone composition for an optical device of the present invention may be prepared by mixing components (a) to (c) and optionally other additives of component (e), comprising components (a) and (b)
  • the parts comprising (a) to (c) and optionally the component (d) except for the part and the component (b) may be prepared separately, and then these two parts may be mixed and prepared.
  • the curable transparent silicone composition for an optical device of the present invention contains the glass silicone compound of the component (a) as a main component, and has a high resilience of the component (b) By proceeding the reaction without aromaticity through the terminal crosslinking agent,
  • the curing of the curable transparent silicone composition for an optical device can be carried out under normal curing conditions, for example, by heating for 30 minutes to 3 hours at 100 to 18 CTC.
  • the Shore D hardness of the cured product obtained by curing the composition is preferably 35 or more, particularly 45 or more, and the curing conditions for making the Shore D hardness of 45 or more are usually 100 to 18C. It can obtain by heating and hardening
  • the organic layer was separated.
  • the separated organic layer was washed repeatedly with a large amount and distilled water and distilled under reduced pressure to obtain 131 g of the final product (6c).
  • the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (PDI) of the compounds prepared in Synthesis Examples 1 to 5 were measured using GPC, and the yields are shown in Table 1 below.
  • the relative vinyl peak value of the Si- O back bone reference peak (Internal standard peak) of the molecule was measured using FT-IR of the compounds prepared in Synthesis Examples 1 to 5, and the vinyl content in the compound was estimated. .
  • Hvinyi height of vinyl absorbance peak (@ 1600-165 ⁇ cm— 1 ⁇
  • H snoxane Si ⁇ height of Si_0 backbone absorbance peak, @ 1940 cm— 1
  • the compound of Synthesis Example 4 showed a weak peak at 2140 nm. This is considered to be due to the residual SiH bonds in the compound molecules prepared in Synthesis Example 4, it is estimated that the response is reduced by the steric hindrance due to such SiH bonds.
  • Synthesis Example 8 Synthesis of Compound of Formula 8c 240.5g (1.0mole, GELEST) and 1,3,5,7-tetramethylcyclotetrasiloxane in a four-necked 1,000 ml reactor equipped with an addition funnel containing a reflux condenser, stirrer, thermometer, and nitrogen injector Methyl disiloxane 3.3g (0.02mole, Wacker) was added and heated to 40 ° C. 0.35 g of trichloromethanesulphonic acid as a catalyst was added to the resultant reactant, followed by vigorous stirring at 40 ° C. for 2 hours, and further distilled water / ethanol 4: 1 mixture was added over 10 minutes, followed by further reaction for 3 hours. I was. Treatment of the resulting reaction product was carried out in the same manner as in Synthesis Example 1 to obtain 212. Og of the final product (8c).
  • each R 1 is a methyl group, X is 40, and y is 1).
  • the viscosity was measured using a Brookfield Corn and Plate Type Viscometer (Brookfield HBDV-II pro, CP5D *).
  • the hardness was measured using a standard resin, in detail, polydimethylsiloxane (PDMS, viscosity 10,000cP, vinyl content 0.3mmole / g) 96 parts by weight, 3 parts by weight of synthetic compounds, 0.5 parts by weight of dimethyl maleate, 0.5 parts by weight of the added semi-aqueous platinum catalyst was mixed and degassed, and cured at 15C C for 2 hours.
  • PDMS polydimethylsiloxane
  • Composite resins 1 to 21 prepared through Table 4 are the main resins, and the hardness of the compounds synthesized in Synthesis Examples 6 to 9 is the highest.
  • the crosslinking agent factor was 1.5, which was obtained by multiplying the amount of the crosslinking agent required by the amount of vinyl resin added to the ratio of the SiH content to the vinyl content.
  • VQM803 TM (HanseChemie, Vinyl 0.21mmole / g) as the main resin, parts by weight corresponding to compound factor 1.5 of Synthesis Example 9 as a crosslinking agent, 0.3 parts by weight of methylbutynol (manufactured by Sigma-Aldrich) as a polymerization inhibitor 0.5 parts by weight of a reactive platinum catalyst (NC25 TM Catalyss, manufactured by Dow Corning Toray), and
  • 0.21 mmole / g is a silicone resin including a Q-unit (quardri-function) and is selected as a comparative example because it is comparable to the products of Synthesis Examples 1 and 2 including some Q 'units.
  • Curing rate, light transmittance, and characteristics of the curable transparent silicone compositions for optical devices prepared in Examples 1 to 21 and Comparative Examples 1 and 2 were cured according to curing conditions.
  • DSC Differential Scanning Calorimetry
  • the fixed temperature was set to 15 CTC, which is a general curing condition, and the curing completion point was defined as a point at which calorie change no longer occurs.
  • the results are shown in FIG.
  • the curable transparent silicone composition for an optical device of Comparative Example 2 including a polymer having a network structure compared to the curable transparent silicone composition for an optical device of Comparative Example 1 composed of only linear polymers
  • curable transparent silicone compositions for optical devices prepared in Examples 1 to 21 and Comparative Examples 1 and 2 were each coated on a glass with a thickness of 1 mm and 2 mm, and then cured at 15 CTC for 2 hours. UV-VIS for the resulting cured film
  • the light transmittance at 600 nm was measured. At this time, the light transmittance at 400 nm is to see the transparency, the light transmittance at 600 nm is to see the degree of yellowing. The results are shown in FIG. 7.
  • the light transmittance was improved regardless of the content of the highly branched siloxane compound.
  • Examples 9 to 10 showed the highest light transmittance improvement.
  • the light transmittance up to Synthesis Example 4 was not reached even if the content was increased, but the resin of Synthetic Resin Synthesis Example 5 used in Examples 13 to 21 also added Synthesis Examples 1 to 4 in small amounts The light transmittance similar to that of the composite resin using Synthesis Example 5 was also improved.
  • Example 10 As shown in FIG. 8, the compositions of Examples 10, 13, 15, and 20 including the highly branched siloxane compound showed higher shear modulus compared to Comparative Examples 1 and 2, and particularly, in Example 10, the glass transition temperature. Gentle starting from It can be seen that the change has the ideal elastic modulus characteristics. In addition, in Example 10 and Example 20 having a high content of the highly branched siloxane compound, the shear modulus of several tens of MPa was maintained even at a high temperature.
  • Adhesive transparent composition for optical devices according to the present invention the curing time is short, exhibits high shear modulus, high crosslinking degree, adhesion strength, surface curing degree and transparency at high temperatures, even after long-term exposure to ultraviolet rays, moisture and heat Transparency can be maintained without fear of discoloration, which is useful as an optical semiconductor adhesive or transparent material.

Abstract

La présente invention concerne une composition de silicium transparente durcissable pour dispositif optique qui est utile en tant que matériau adhésif ou transparent pour un semi-conducteur optique, la composition de silicium transparente durcissable ayant un temps de durcissement court et présentant un module de cisaillement élevé, un degré élevé de réticulation, de contrainte d'adhésion, de durcissement de surface, et de transparence à une température élevée, et maintient la transparence sans risque de décoloration, même après exposition à la lumière ultraviolette, l'humidité et la chaleur pendant une longue période en subissant une réaction de réticulation sans directivité par l'intermédiaire d'un agent de réticulation de type terminal ayant une réactivité élevée, et en utilisant un composé de silicium organique sous une forme régulière et hautement ramifiée en tant que composant principal.
PCT/KR2013/010899 2012-11-30 2013-11-28 Composition de silicium transparente durcissable pour dispositif optique WO2014084624A1 (fr)

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KR20040078024A (ko) * 2003-03-03 2004-09-08 주식회사 금강고려화학 부가경화형 실리콘 감압 접착제 조성물
KR20070097075A (ko) * 2005-01-24 2007-10-02 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 발광 소자 밀봉용 실리콘 조성물과 발광 장치
KR20080007152A (ko) * 2006-07-14 2008-01-17 신에쓰 가가꾸 고교 가부시끼가이샤 경화성 실리콘 고무 조성물 및 그의 경화물
KR20090054429A (ko) * 2006-08-25 2009-05-29 다우 코닝 도레이 캄파니 리미티드 경화성 오가노폴리실록산 조성물 및 반도체 장치
KR20100134516A (ko) * 2009-06-15 2010-12-23 신에쓰 가가꾸 고교 가부시끼가이샤 다이본딩용 실리콘 수지 조성물

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Publication number Priority date Publication date Assignee Title
KR20040078024A (ko) * 2003-03-03 2004-09-08 주식회사 금강고려화학 부가경화형 실리콘 감압 접착제 조성물
KR20070097075A (ko) * 2005-01-24 2007-10-02 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 발광 소자 밀봉용 실리콘 조성물과 발광 장치
KR20080007152A (ko) * 2006-07-14 2008-01-17 신에쓰 가가꾸 고교 가부시끼가이샤 경화성 실리콘 고무 조성물 및 그의 경화물
KR20090054429A (ko) * 2006-08-25 2009-05-29 다우 코닝 도레이 캄파니 리미티드 경화성 오가노폴리실록산 조성물 및 반도체 장치
KR20100134516A (ko) * 2009-06-15 2010-12-23 신에쓰 가가꾸 고교 가부시끼가이샤 다이본딩용 실리콘 수지 조성물

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