WO2014084624A1 - Curable transparent silicon composition for optical device - Google Patents

Curable transparent silicon composition for optical device 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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French (fr)
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/en
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Publication of WO2014084624A1 publication Critical patent/WO2014084624A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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

The present invention provides a curable transparent silicon composition for an optical device which is useful as an adhesive or transparent material for an optical semiconductor, wherein the curable transparent silicon composition has a short curing time and exhibits a high shear modulus, a high degree of cross-linking, adhesive stress, surface hardening, and transparency at a high temperature, and maintains transparency without the possibility of discoloration even after being exposed to ultraviolet light, humidity, and heat for a long period of time by undergoing a cross-linking reaction without directivity through a terminal-type cross-linking agent having high reactivity and by using an organic silicon compound in a regular and highly branched form as a main ingredient.

Description

명세서  Specification
발명의 명칭: 광디바아스용 경화형 투명 실리콘 조성물  Name of invention: Curable transparent silicone composition for optical devices
기술분야 Field of technology
본 발명은 광디바이스용 경화형 투명 실리콘 조성물에 관한 것이다. 배경기술  The present invention relates to a curable transparent silicone composition for an optical device. Background
전자 기기， OA 기기， 자동차， 정밀기기， 건축 재료 등의 접착 또는 밀봉 을 위한 접착제 또는 밀봉제로서 폴리우레탄 수지， 아크릴계 수지， 에폭시 수지， 실리콘 수지 등의 다양한 수지가 사용되고 있다. 최근 광학 부품의 소형화나 광원의 고휘도화에 대해 내열성 및 내광성이 우수한 투명 유기 수지 재료에 대한 요구가 증가함에 따라， 통상의 접착 또는 밀봉용 수지 들에 비해 우수한 내열 및 내한성, 전기 절연성， 내후성, 발수성 및 투명 성을 가지며， 변색의 우려 및 물리적 열화의 우려가 낮은 실리콘계 수지 의 광학 부품 재료， 특히 광반도체 소자의 접착제로서의 용도가 기대되고 있다.  Various resins such as polyurethane resins, acrylic resins, epoxy resins, and silicone resins are used as adhesives or sealants for bonding or sealing electronic devices, OA devices, automobiles, precision devices, and building materials. In recent years, as the demand for transparent organic resin materials having excellent heat resistance and light resistance for miniaturization of optical components and high brightness of light sources has increased, superior heat and cold resistance, electrical insulation, weather resistance, and water repellency than conventional adhesive or sealing resins have increased. And silicone resins having transparency and low risk of discoloration and physical deterioration are expected to be used as adhesives for optical component materials, particularly optical semiconductor elements.
이에 따라 용도에 따른 실리콘계 수지의 물성을 개량하기 위한 다양한 방법들이 연구되고 제안되었다. 구체적인 예로， 일본특허공개 제 2004- 186168호 및 일본특허공개 제 2006-202952호에는 규소 원자 결합 알케 닐기와 규소 원자에 결합한 수소 원자 사이의 히드로 실릴화 반응에 의하 여 경화하는 부가 경화형 실리콘 수지 조성물이 개시되어 있고， 일본특허 공개 제 2006-342200호에는 상기 부가 경화형 실리콘 수지 조성물의 제 조시 유기폴리실록산으로서 규소 원자 결합 알케닐기를 가지며， 점도가 lOOOmPa - s 이하인 직쇄상 유기폴리실록산과 23 °C에서 밀랍상 또는 고 체인 삼차원 망상 유기폴리실록산 수지를 이용하여 고경도이며， 내열성， 투명성 및 저파장 영역에서의 광투과성이 우수한 다이 본딩용 실리콘 수 지 조성물이 개시되어 있으며, 일본특허공개 제 2008-031190호는 상기 부가 경화형 실리콘 수지를 포함하는 경화형 실리콘 조성물 중에 무기이 은교환체를 사용하여 금속 부재의 황화에 의한 부식 발생을 억제하는 방 법이 개시되어 있다. Accordingly, various methods for improving the physical properties of the silicone resin according to the use have been studied and proposed. As a specific example, 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. with a linear organic polysiloxane having a viscosity of lOOOOmPa-s or less. Or 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, and 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.
그러나， 상기 부가 경화형 실리콘 수지 조성물에서 베이스 수지로 사용 된 규소원자에 결합된 알케닐기를 포함하는 유기 폴리실록산은 70 내지 100°C의 저은에서 말단끼리 우선 반웅하여 사슬을 형성하는 1차 경화를 거친 후， 150°C 이상의 고온에서 반응성이 낮은 측쇄부가 반웅하여 가교 를 형성하는 2차경화를 거치게 되는데， 이와 같이 급격한 고은 경화시 무 거운 구조가 가벼운 구조에 매달리는 형태로 가교가 형성되게 됨으로써 잔류내부응력이 증대되어 물성이 저하되는 문제가 있다. However, in the addition-curable silicone resin composition, 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. As such, 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.
또한， 일본특허공개 제 2005— 005614호에는 1분자 중에 2개 이상의 에 폭시기를 갖고， 분자량이 500 이상 2，100 이하인 실리콘 화합물， 산무수 물， 그리고 촉매를 포함하여， 접착성， 내열성， 내습성이 우수한 동시에， 저 웅력의 열경화형 수지 조성물이 개시되어 있고， 일본특허공개 제 2006- 077234호에는 폴리스티렌 환산의 중량평균 분자량이 5xl03g/mol 이상인 특정 구조의 오르가노폴리실록산， 및 축합 촉매를 함유하여 내열성， 내 자 외선성， 광학적 투명성， 강인성 및 접착성을 개선시킨 LED 소자 봉지용 수지 조성물이 개시되어 있다. In addition, 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. At the same time, 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.
또한， 미국공개특허 제 2007— 0298223호에는 열에 의해 활성화된 오가 노보란 아민 착물의 존재하에 경화되거나， 유리 라디칼 증합성 오가노실 리콘 단량체， 을리고머 또는 중합체， 및 오가노보란 아민 착물과 아민 반 웅성 화합물을 산소 함유 환경 속에서 배합함으로써 경화되는 유리 라디 칼 중합성 오가노실리콘 단량체， 을리고머 또는 중합체를 함유하는 경화 형 조성물이 개시되어 있고， 국제공개특허 계 WO2007/100445호에는 알케 닐 작용성 페닐 함유 폴리오가노실톡산， Si-H 작용성 페닐 함유 폴리오가 노실록산， 또는 이들의 조합물; 비분자량을 갖는 하이드로겐디오가노실록 시 말단화 올리고디페닐실록산， 비분자량을 갖는 알케닐 작용성 디오가노 실록시 -말단화 올리고디페닐실록산， 또는 이들의 조합물; 그리고 하이드 로실릴화 촉매를 포함하여， 경화시 광학적 투명도， 높은 굴절를， 고온에 대한 내성 및 높은 기계적 강도를 갖는 실리콘 제품을 형성함으로써 발광 장치 적용시 신뢰성을 향상시킬 수 있는 하이드로실릴화-경화형 조성물이 개시되어 있다.  In addition, 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; Non-molecular weight hydrogendiorganosiloxane terminated oligodiphenylsiloxanes, non-molecular weight alkenyl functional diorgano siloxy-terminated oligodiphenylsiloxanes, or combinations thereof; And 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.
또한 미국등록특허 제 5，982，041호에는 고 에너지 복사로의 노출에 의 해 유도되는 아크릴 작용성 오가노폴리실록산의 유리 라디칼 반웅과， 알 케닐 작용성 오가노폴리실록산과 실리콘 결합된 수소 작용성 오가노폴리 실록산과의 하이드로실릴화 반웅을 통해 경화되는 실리콘 다이 부착 접착 제용 실록산 조성물이 개시되어 있다.  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.
한국등록특허 제 377590호에는 (a) 각 분자에 규소 원자에 결합된 2개 이상의 알콕시기를 함유하고， 규소 원자에 결합된 알케닐기를 함유하지 않는 오르가노폴리실록산 및 각 분자에 규소 원자에 결합된 2개 이상의 알케닐기를 함유하고， 규소 원자에 결합된 알콕시기를 함유하지 않는 오 르가노폴리실록산의 흔합물， 또는 (b) 각 분자에 규소 원자에 결합된 2개 W 201 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. A mixture of organopolysiloxanes containing at least two alkenyl groups and free of alkoxy groups bonded to silicon atoms, or (b) two bonded to silicon atoms in each molecule W 201
3 이상의 알콕시기 및 규소 원자에 결합된 2개의 알케닐기를 각각 함유하는 오르가노폴리실록산; 각 분자에 규소 원자에 결합된 2개 이상의 수소 원 자를 함유하는 오르가노폴리실록산; 축합 반웅 촉매; 및 백금형 촉매와 함께， 공기-산화-경화형 불포화 화합물을 포함하여 히드로실릴화 반웅 및 축합 반응에 의해 경화시 무광택 특성이 우수한 경화 제품을 형성함으로 써 발광 다이오드 디스플레이 장치에 유용한 경화형 실리콘 조성물이 개 시되어 있다.  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. There is.
미국공개특허 제 2008— 0185601호에는 알케닐 그룹과 페닐 그룹을 포함 하고, 폴리스티렌을 참조물질로 하여 겔 크로마토그래피에 의해 측정한 중량 평균 분자량이 3000 이상인 오가노폴리실록산 수지 ; 알케닐 그룹 및 페닐 그룹을 포함하는 오가노올리고실록산; 특정 구조의 오가노하이드 로겐을리고실록산 또는 오가노하이드로겐폴리실록산; 부가 반웅형 촉매; 및 이형제를 포함하여， 경화시 25°C에서 경화도 60 내지 100， 및 150°C 에서 경화도 40 내지 10CKASTM D2240-86에 의해 측정 )을 나타내는 제 품을 형성할 수 있는 부가 경화형 오가노폴리실록산 수지 조성물이 개시 되어 있다. 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.
또한 국제공개특허 제 WO2006/077667호에는 특정 구조의 3차원 그물 형상 구조의 비닐기 함유 오르가노폴리실록산; 1분자 중에 적어도 2개의 규소 원자 결합 수소 원자를 갖는 오르가노하이드로젠폴리실록산; 그리고 히드로실릴화 반웅 촉매를 포함하여， 경화 후 10~290xl0_6rc의 선 팽창 계수를 갖는 경화물을 형성할 수 있는 발광 소자 밀봉용 실리콘 조성물이 개시되어 있다. In addition, 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.
또한， 한국등록특허 제 704883호에는 하나 이상의 폴리오르가노실록산 과 부가 반웅형 촉매를 포함하여 경화시 수지성 물질이 되는 LED 캡슐화 조성물이 개시되어 있다.  In addition, 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.
이와 같이 광학부품의 용도에 따라 요구되는 물성적 요건을 충족하기 위해서는 해당 용도에 대해 최적화한 구성을 갖는 실리콘 수지 조성물을 개발하는 것이 중요하다.  As such, in order to meet the physical property requirements required for the use of the optical component, it is important to develop a silicone resin composition having a configuration optimized for the use.
발명의 상세한 설명 Detailed description of the invention
기술적 과제 Technical challenges
본 발명의 목적은 경화시간이 짧고， 고온에서의 높은 전단탄성률， 높은 가교도， 접착웅력， 표면 경화도 및 투명도를 나타내며， 장기간 자외선， 습 기 및 열에 노출된 후에도 변색의 우려 없이 투명성을 유지할 수 있어 광 반도체용 접착제 또는 투명 소재로서 유용한 광디바이스용 경화형 투명 실리콘 조성물을 제공하는 것이다. 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.
과제 해결 수단 Challenge solution
본 발명의 일 구현예에 따르면， 유기 실리콘 화합물, 가교제, 및 부가반
Figure imgf000006_0001
According to one embodiment of the present invention, an organic silicone compound, a crosslinking agent, and an addition group
Figure imgf000006_0001
Figure imgf000006_0002
이루어진 군에서 선택되 는 결합 구조를 포함하고， 분자 중 규소원자 (Si)에 직접 결합되거나 또는 산소원자 (0)를 통해 Si에 결합된 탄소수 2 내지 10의 알케닐기를 3개 이 상의 포함하며， 분자내 비닐함량이 0.1 내지 20mmole/g인 분지쇄상 또는 삼차원 망상 구조의 유기 실록산 화합물을 포함하는 것인 광디바이스용 경화형 투명 실리콘 조성물을 제공한다.
Figure imgf000006_0002
Including 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), Provided is 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.
상기 광디바이스용 경화형 투명 실리콘 조성물에 있어서， 상기 유기 실 리콘 화합물은 하기 (a-1)의 제 1 유기 실리콘 화합물, (a-2)의 제 2유기 실록산 화합물 및 이들의 흔합물로 이루어진 군에서 선택되는 것일 수 있 다:  In the curable transparent silicone composition for an optical device, 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) 하기 화학식 la 내지 lc의 화합물로 이루어진 군에서 선택되는 제 1 유기 실리콘 화합물; 그리고  (a-1) a first organosilicon compound selected from the group consisting of compounds of the formula la to lc; And
(a-2) 단위 분자 내 규소를 포함하고， Q-유닛 (quardri— function functional siloxane group), 또는 Q一유 과 T一유 (Tri— functional siloxane group)의 흔합구조를 포함하며， 분자내에 Si에 직접 결합된 탄소수 2 내지 10의 알케닐기를 3개 이상의 포함하는 하기 화학식 4의 제 2유기 실록산 화합물.  (a-2) containing silicon in a unit molecule, including a Q-unit (quardri—functional functional siloxane group), or a mixed structure of Ql- and Tl- (tri-functional siloxane group); A second organic siloxane compound of formula (4) comprising three or more alkenyl groups directly bonded to:
[화학식 la]
Figure imgf000006_0003
[Formula la]
Figure imgf000006_0003
(상기 화학식 la에서,  (In the above formula la,
a, b 및 c는 각각 정수로서， 0≤a≤3, 0≤b≤3, 0<c≤3이고
Figure imgf000006_0004
(이때， R'은 탄소수 2 내지 10의 알케닐기이고 a, b and c are integers, respectively, 0≤a≤3, 0≤b≤3, and 0 <c≤3.
Figure imgf000006_0004
Where R 'is an alkenyl group having 2 to 10 carbon atoms
또는 1의 정수이다)이며ᅳ - RCYRIf Or an integer of 1) -R C YRI f
RCR& RRIIII  RCR & RRIIII
X는  X is
RCRII
Figure imgf000007_0001
들의 조합으로 이루어진 군에서 선택되며 RCRII (이때， R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기, 히드록시기, 탄소수 1 내지 20의 알콕시기, 에폭시기， 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알킬기이다) 및 이들의 조합으로 이루어진 군에서 선택된다), 그리고 RCRII
Figure imgf000007_0001
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) An alkoxy group, an epoxy group, an amino group of from 20 to (-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
Y 및 Z는 각각 독립적으로 탄소수 1 내지 20의 지방족 포화  Y and Z are each independently aliphatic saturation having 1 to 20 carbon atoms
탄화수소기， 탄소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 히드록시기， 에폭시기， 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 및 하기 화학식 2의 작용기로 이루어진 군에서 선택된다: 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):
[화학식 2]  [Formula 2]
Figure imgf000007_0002
Figure imgf000007_0002
상기 화학식 2에서， b, c, T, X 및 Y는 앞서 정의한 바와 동일하다) [화학식 lb]  In Formula 2, b, c, T, X and Y are the same as defined above) [Formula lb]
Figure imgf000007_0003
(상기 화학식 lb에서，
Figure imgf000007_0003
(In the formula lb,
e, f 및 g는 각각 정수로서 0<e≤100, l≤f<5, 0<g≤2이고， 덴드리머 구조로 표현시 제너레이션 (generation) 수가 2 이하이며，  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,
R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 히드톡시기， 탄소수 1 내지 20의 알콕시기， 에폭시기， 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알킬기이다) 및 이들의 조합으 이루어진 군에서 선택되고， 그리고 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
T는 *"(0)lR (이때， R '은 탄소수 2 내지 10의 알케닐기이고 , ζ는 0 또는 1의 정수이다)이며， T is * " ( 0 ) l R (wherein R 'is an alkenyl group having 2 to 10 carbon atoms, ζ is an integer of 0 or 1),
단， 상기 R과 Τ는 화학식 lb의 화합물 분자내 탄소수 2 내지 10의 알케닐기의 수가 3개 이상이 되도록 선택된다)  Wherein R and Τ 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)
[화학식 lc]  [Formula lc]
Figure imgf000008_0001
Figure imgf000008_0001
(상기 화학식 lc에서，  (In Chemical Formula lc,
h, i 및 j는 각각 정수로서 0 h<100, l<i≤5, 0<j<2이고，  h, i and j are each an integer of 0 h <100, l <i ≦ 5, 0 <j <2,
R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 히드록시기, 탄소수 1 내지 20의 알콕시기， 에폭시기, 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알킬기이다) 및 이들의 조합으로 이루어진 군에서 선택되고 그리고 T는 、 'ζ (이때， R'은 탄소수 2 내지 10의 알케닐기이고 , ζ는 0 또는 1의 정수이다)이며, 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 ' ζ (wherein R' is an alkenyl group having 2 to 10 carbon atoms, ζ is an integer of 0 or 1),
단, 상기 R과 Τ는 화학식 lc의 화합물 분자내 탄소수 2 내지 10의 알케닐기의 수가 3개 이상이 되도록 선택된다)  Wherein R and Τ 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)
[화학식 4]  [Formula 4]
(R3Si)a(Si04/2)b(R2Si01/2)c(Si03/2)d(R3Si)e (R 3 Si) a (Si0 4/2 ) b (R 2 Si0 1/2 ) c (Si0 3/2 ) d (R 3 Si) e
(상기 화학식 4에서，  (In Formula 4,
a, b, c, d 및 e는 각각 정수로서， l<a<30, l<b<20, 0<c<30, 0<d<10 및 l≤e≤30이고， 그리고 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
R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 히드톡시기， 탄소수 1 내지 20의 알콕시기， 에폭시기， 아미노기 (ᅳ NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알킬기이다) 및 이들의 조합으로 이루어진 군에서 선택되며， 단， 상기 R중 적어도 3개는 탄소수 2 내지 10의 알케닐기이다) 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)
또, 상기 제 1 유기 실리콘 화합물은 하기 화학식 3a 내지 3c의  In addition, the first organosilicon compound is represented by the formulas 3a to 3c
화합물로 이루어진 군에서 선택되는 것일 수 있다: It may be selected from the group consisting of compounds:
[화학식 3a]  [Formula 3a]
Figure imgf000009_0001
Figure imgf000009_0001
[화학식 3b]
Figure imgf000010_0001
[Formula 3b]
Figure imgf000010_0001
[화학식 3c]  [Formula 3c]
Figure imgf000010_0002
Figure imgf000010_0002
(상기 식에서， m 및 n은 각각 독립적으로 0 내지 100의 정수이다.) 그리고， 상기 광디바이스용 경화형 투명 실리콘 조성물에 있어서， 상기 제 2유기 실록산 화합물은 분자내에 Q-유닛 (Si04/2), 또는 Q-유닛과 T- 유닛 (Si03/2)을 포함하는 분지상 반복단위 (branched unit)를 3 내지 30개 포함하고， 터미널 유닛 (terminal unit)으로서 -Si!^I^R^이때， R1 및 R2는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고， R3은 탄소수 2 내지 10의 알케닐기임)을 포함하는 3차원 망목 구조의 유기 실록산 화합물일 수 있다. (In the above formula, m and n are each independently an integer of 0 to 100.) In the curable transparent silicone composition for an optical device, 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.
또， 상기 제 2유기 실록산 화합물은 하기 화학식 6a 내지 6c의 화합물로 이루어진 군에서 선택되는 것일 수 있다: '  In addition, the second organic siloxane compound may be selected from the group consisting of compounds represented by the following Chemical Formulas 6a to 6c:
[화학식 6a] 30의 정수이다) [Formula 6a] Is an integer of 30)
Figure imgf000011_0001
Figure imgf000011_0001
[화학식 6c]  [Formula 6c]
Figure imgf000011_0002
Figure imgf000011_0002
(상기 화학식 6c에서， m은 1 내지 10의 정수이고， n은 2 내지 30의 정수이다)  (In Chemical Formula 6c, m is an integer of 1 to 10, n is an integer of 2 to 30)
또， 상기 제 2유기 실록산 화합물은 25°C에서의 점도가 100mPa - s 이상의 액상 또는 고체상일 수 있다. In addition, the second organic siloxane compound may have a viscosity at 25 ° C. of 100 mPa-s or more in liquid or solid form.
그리고， 상기 광디바이스용 경화형 투명 실리콘 조성물에 있어서， 상기 가교제는 하기 화학식 7의 반복단위를 포함하며， 규소원자에 결합한 수소원자를 1분자 중에 2개 이상 포함하는 제 3유기 실록산 화합물일 수 있다： And in the curable transparent silicone composition for the optical device, 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:
[화학식 7]  [Formula 7]
-(R1pHqSiO(4.p-q)/2)- 상기 화학식 7에서， In Formula 7, - - (R1pHqSiO (4 .pq) / 2)
p 및 q은 정수로서 0<p<4, 0<q<4이면서 0<p+q<4이고， 그리고  p and q are integers 0 <p <4, 0 <q <4 and 0 <p + q <4, and
R1은 각각 독립적으로 탄소수 1 내지 10의 알킬기, 할로겐기, 탄소수 1 내지 10의 할로알킬기， 히드록시기 및 시아노기로 이루어진 군에서 선택되는 치환기로 치환되거나 또는 비치환된， 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 및 이들의 조합으로 이루어진 군에서 선택된다. 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.
또， 상기 가교제는 하기 화학식 8a 내지 8d의 화합물로 이루어진 군에서 선택돠는 것일 수 있다:  In addition, the crosslinking agent may be selected from the group consisting of compounds of the formula 8a to 8d:
[화학식 8a]  [Formula 8a]
Figure imgf000012_0001
Figure imgf000012_0001
[화학식 8b]  [Formula 8b]
Figure imgf000012_0002
Figure imgf000012_0002
[화학식 8d]
Figure imgf000013_0001
[Formula 8d]
Figure imgf000013_0001
상기 화학식 8a 내지 8d에서，  In Chemical Formulas 8a to 8d,
R1은 각각 독립적으로 탄소수 1 내지 10의 알킬기， 할로겐기， 탄소수 1 내지 10의 할로알킬기, 히드록시기 및 시아노기로 이루어진 군에서 선택되는 치환기로 치환되거나 또는 비치환된， 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 및 이들의 조합으로 이루어진 군에서 선택되고， 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;
V는 1 내지 20의 정수， w는 1 내지 10ᄋ의 정수， X는 0 내지 100의 정수， 그리고 y는 1 내지 50의 정수이다. V is an integer from 1 to 20, w is an integer from 1 to 10 0, X is an integer from 0 to 100, and y is an integer from 1 to 50.
또， 상기 가교제는 25°C에서의 점도가 l,000mPa - s 이하인 것일 수 있다. In addition, the crosslinking agent may have a viscosity at 25 ° C. of less than l, 000 mPa-s.
또， 상기 가교제는， 가교제 분자 중 규소 원자에 결합한 수소원자가 상기 유기 실리콘 화합물 중의 전체 규소 원자에 결합한 알케닐기에 대하여 0.5 내지 3배 몰이 되는 양으로 포함될 수 있다.  In addition, 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.
또， 상기 가교제는 상기 유기 실리콘 화합물 100중량부에 대하여 1 내지 15중량부로 포함될 수 있다.  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.
그리고， 상기 광디바이스용 경화형 투명 실리콘 조성물에 있어서, 상기 부가 반웅형 촉매는 백금족 금속 촉매일 수 있다.  In addition, in the curable transparent silicone composition for an optical device, the addition semi-heunggung catalyst may be a platinum group metal catalyst.
또， 상기 부가 반응형 촉매는 유기 실리콘 화합물 총 중량에 대하여 백금족 금속 원소의 질량 환산으로 10 내지 5000ppm의 양으로 포함될 수 있다.  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.
그리고， 상기 광디바이스용 경화형 투명 실리콘 조성물은 유리 위에 두께 1mm 내지 2mm로 도포 후 경화시 유리 광투과도 대비 450nm 및 600nm에서 90% 이상의 광투과도를 나타내는 것일 수 있다.  In addition, 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.
또， 상기 광디바이스용 경화형 투명 실리콘 조성물을 두께 2mm로 경화시 전단탄성률이 25°C에서 150Mpa 이하이고， 100°C 이상의 In addition, 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
온도에서 20Mpa 이상일 수 있다. The temperature may be at least 20 Mpa.
기타 본 발명의 구현예들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다. Other details of embodiments of the present invention are described in the following detailed description. Included.
발명의 효과 Effects of the Invention
본 발명에 따른 광디바이스용 접착성 투명 조성물은， 규칙성 고가지화 형태의 유기 실리콘 화합물을 주재로 이용하고 반응성이 큰 말단형 가교 제를 통해 방향성 없이 가교반응을 진행함으로써， 경화시간이 짧고， 고온 에서의 높은 전단탄성률， 높은 가교도， 접착웅력， 표면 경화도 및 투명도 를 나타내며， 장기간 자외선， 습기 및 열에 노출된 후에도 변색의 우려 없 이 투명성을 유지할 수 있어 광반도체용 접착제 또는 투명 소재로서 유용 하다.  The adhesive transparent composition for an optical device according to the present invention 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. .
도면의 간단한 설명 Brief description of the drawings
도 1 내지 5는 각각 합성예 1 내지 5의 화합물에 대한 FT-IR(Fourier Transform Infrared Spectroscopy) 관찰 결과를 나타낸 그래프이다. 도 6은 실시예 1 내지 21 및 비교예 1,2의 광디바이스용 경화형 투명 실리콘 조성물에 대한 고정온도 (150°C)에서꾀 경화완료지점을 관찰한 결 과를 나타낸 그래프이다. 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.
도 7은 실시예 1 내지 21 및 비교예 1，2의 광디바이스용 경화형 투명 실리콘 조성.물을 경화시킨 후， 광투과도를 측정한 결과를 나타낸 그래프 이다.  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.
도 8은 실시예 10， 13， 15， 20, 및 비교예 1，2의 광디바이스용 경화형 투명 실리콘 조성물을 경화시킨 후， 전단탄성율올 측정한 결과를 나타낸 그래프이다.  8 is a graph showing the results of measuring the shear modulus after curing the curable transparent silicone composition for optical devices of Examples 10, 13, 15, 20, and Comparative Examples 1, 2;
발명의 실시를 위한 최선의 형태 Best Mode for Carrying Out the Invention
이하， 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이 하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그 러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설 명하는 실시예에 한정되지 않는다.  Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
본 명세서에서 특별한 언급이 없는 한 모든 화합물 또는 치환기는 치환 되거나 비치환된 것일 수 있다. 여기서， '치환된'이란 수소가 할로겐기， 하이드록시기， 카르복시기, 시아노기， 니트로기， 아미노기， 티오기， 메틸티 오기， 알콕시기ᅳ 알데하이드기， 에폭시기, 에테르기， 에스테르기， 카르보닐 기， 아세탈기， 케톤기， 알킬기， 퍼플루오로알킬기， 시클로알킬기, 헤테로시 클로알킬기， 알릴기， 벤질기， 아릴기， 헤테로아릴기， 이들의 유도체 및 이 들의 조합으로 이루어진 군에서 선택되는 어느 하나로 대체된 것을 의미 한다. Unless specifically stated herein, all compounds or substituents may be substituted or unsubstituted. Herein, '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.
본 명세 o서에서 '이들의 조합'이란 특별한 언급이 없는 한， 둘 이상의 작 용기가 단일결합， 이중결합 (에틸렌기)， 삼중결합 (아세틸렌기)， 탄소수 1 내 지 20의 알킬렌T I기 (예를 들면， 메틸렌 (-CH2-), 에틸렌 (-CH2CH2-), 등)， 탄소수 1 내지 20의 플루오로알킬렌기 (예를 들면， 플루오로메틸렌 (-CF2— )， 플루오로에틸렌 (-CF2CF2-) 등), N, 0， P, S, 또는 Si와 같은 헤테로 원 자 또는 이를 포함하는 작용기 (구체적으로는, 분자내 카르보닐기 (-C=0-), 에테르 (ether, -0-), 에스테르 (ester, -COO— ), -S-, 아민기 (-NH ) 또는 - -N=N- 등을 포함하는 헤테로알 0킬렌기)와 같은 연결기에 의해 결합되어 있거나， 또는 둘 이상의 작용기가 축C II합， 연결되어 있는 것을 의미한다. 본 발명은 (a) 유기 실리콘 화합물， (b) 가교제， 및 (c) 부가반웅형 촉매 를 이용하여 광디바이스용 경화형 투명 실리콘 조성물의 제조시， 상기 (a) 유기 실리콘 화합물로서 단위 분자 내에 규소 ―—원자를 포함하고 적어도 3개 이상의 가교점을 가진 규칙성 고가지화 형태의 유기 실리콘 화합물을 이 용함으로써， 종래 실리콘 화합물의 말단과 측쇄부의!丄〕 I 반응사이트로 가교반 응을 형성하는 종래와는 달리, 방향성 없이 가교 반웅이 진행되기 때문에 경화시간이 짧고， 고온에서의 높은 전단탄성률， 높은 가교도， 접착응력， 표면 경화도 및 투명도를 나타내며， 장기간 자외선， 습기 및 열에 노출된 후에도 변색의 우려 없이 투명성을 유지할 수 있어 광반도체용 C ——접착제 또 는 투명 소재로서 유용한 것을 특징으로 한다. C II In this specification o standing "combinations thereof" it means special Unless noted, is a single bond two or more smaller containers, a double bond (ethylene group), a triple bond (acetylene group), C 1 within the support 20 of alkylene T I group (For example, methylene (-CH 2- ), ethylene (-CH 2 CH 2- ), etc.), fluoroalkylene groups having 1 to 20 carbon atoms (for example, fluoromethylene (-CF 2 —), Heteroatoms such as fluoroethylene (-CF 2 CF 2- ), N, 0, P, S, or Si or a functional group comprising the same (specifically, an intramolecular carbonyl group (-C = 0-), By a linking group such as ether (ether, -0-), ester (ester, -COO—), -S-, amine group (-NH), or heteroal 0-chelene group including--N = N- It means that it is bonded, or that two or more functional groups are condensed C II sum. 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丄] 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. C II
이하 각 성분 별로 보다 상세히 설명한다.  Hereinafter, each component will be described in more detail.
성분 (a)  Component (a)
상기 성분 (a)의 유기 실리콘 화합물은 단위 분자 내에  The organosilicon compound of component (a) is contained within a unit molecule
Figure imgf000015_0001
이루어진 군에서 선택되 는 결합 구조를 포함하고， 분자 중에 Si와 직접 결합되거나 또는 산소원 자 (0)를 통해 Si에 결합된 탄소수 2 내지 10의 알케닐기를 3개 이상 포 함하며， 분자내 비닐함량이 0.1 내지 20mmole/g, 바람직하게는 0.5 내지 12mmole/g인 분지 또는 삼차원 망상 구조의 유기 실록산 화합물일 수 있다. 상기 비닐함량이 0.1mmole/g 미만인 경우 조성물 내에서 가교도를 떨 어뜨려 전단탄성률 및 접착력을 저하시키고， 20mmole/g을 초과할 경우 조성물 내에서 경화 후 쉽게 부서지거나， 또는 열에 의해 쉽게 황변될 수 있다.
Figure imgf000015_0001
Including 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. When 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. When 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. .
또 상기 성분 (a)의 유기 실리콘 화합물은 분지쇄 또는 삼차원 망상 구 조의 일례로서 덴드리머 구조를 가질 수 있으며， 이 경우 그 제너레이션 수가 3 이하인 것이 바람직할 수 있다. 만약 제너레이션수가 3을 초과하 면 가교반웅 및 경화 속도의 제어가 어려울 수 있으며， 합성단계가 늘어 나 상업화가 어려울 수 있다.  In addition, 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.
구체적으로는， 상기 성분 (a)의 유기 실리콘 화합물은 하기 (a-l)의 제 1 유기 실리콘 화합물, 하기 (a-2)의 제 2유기 실록산 화합물 및 이들의 흔 합물로 이루어진 군에서 선택되는 것일 수 있다:  Specifically, 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:
(a-l) 제 1 유기 실리콘 화합물  (a-l) First Organic Silicon Compound
상기 제 1 유기 실리콘 화합물은 분자내에 Si에 직접 결합되거나 또는 산소원자 (0)를 통해 Si에 결합된 탄소수 2 내지 10의 알케닐기， 보다 바 람직하게는 비닐기를 3개 이상의 포함하는， 분지 또는 삼차원 망상 구조 의 폴리실록산 화합물 또는 폴리카보실록산 화합물일 수 있다. 보다 구체 적으로는 하기 화학식 la 내지 lc의 화합물로 이루어진 군에서 선택되는 것일 수 있다:  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:
[화학식 la] [Formula la]
Figure imgf000016_0001
Figure imgf000016_0001
[화학식 lb]
Figure imgf000016_0002
[화학식 lc] [Formula lb]
Figure imgf000016_0002
[Formula lc]
, 0<c<3이고， 0의 ¾ RRII알케닐기일 , 0 <c <3, and ¾ RRII alkenyl group of 0
바 이다)이 RCRII며，
Figure imgf000017_0001
Is RCRII,
Figure imgf000017_0001
Figure imgf000017_0002
및 이들의 조합으로 이루어진 군에서 선택되는 것일 수 있고 (이때 R은 각각 독립적으로 탄소 수 1 내지 20의 알킬기 (예를 들면, 메틸기， 에틸기， 프로필기， 이소프로필 기， 부틸기， 이소부틸기, t-부틸기 등) 또는 탄소수 3 내지 20의 사이클로 알킬기 (예를 들면, 사이클로프로필기， 사이클로부틸기， 사이클로핵실기 등) 등을 포함하는 탄소수 1 내지 20의 지방족 포화 탄화수소기; 탄소수 2 내지 10의 알케닐기 (예를 들면， 에테닐기， 프로펜일기， 부테닐기 등)， 탄소수 2 내지 10의 알키닐기 (예를 들면, 에티닐기， 프로피닐기， 부티닐기 등)， 또는 탄소수 3 내지 20의 사이클로알케닐기 등올 포함하는 탄소수 2 내지 20의 지방족 불포화 탄화수소기 ; 탄소수 6 내지 30의 아릴기 (예를 들면, 페닐기 등)를 포함하는 탄소수 6 내지 30의 방향족 탄화수소기 ; 히 드록시기; 탄소수 1 내지 20의 알콕시기 (예를 들면， 메톡시기， 에록시기, W
Figure imgf000017_0002
And combinations thereof, wherein 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 hydrocarbon group containing alkenyl group etc .; C6-C30 aromatic carbonized water containing the aryl group (for example, phenyl group) of 6-30 carbon atoms Group; Hi deurok group; an alkoxy group (e.g., methoxy group, erok group having 1 to 20 carbon atoms, W
16 프로폭시기, t-부특시기 등); 에폭시기; 아미노기 (― NRaRb, 이때 Ra 및 Rb 는 각각 독립적으로 메틸기 , 에틸기 둥의 탄소수 1 내지 5의 알킬기임); 및 이들의 조합으로 이루어진 군에서 선택되는 것이며， 바람직하게는 탄 소수 1 내지 10의 알킬기， 탄소수 2 내지 10의 알케닐기， 탄소수 6 내지 18의 아릴기， 히드록시기， 에폭시기， 아미노기 및 이들의 조합으로 아루어 진 군에서 선택되는 것일 수 있다)， 16 propoxy group, t-subspecialty, etc.); Epoxy groups; Amino groups (—NR a R b , wherein R a and R b are each independently a methyl group, an alkyl group having 1 to 5 carbon atoms in an ethyl group); And combinations thereof, and preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxy group, an epoxy group, an amino group, and a combination thereof. Can be chosen from the Lun-gun group) ，
Y 및 Z는 각각 독립적으로 탄소수 1 내지 20의 알킬기 (예를 들면， 메 틸기， 에틸기， 프로필기， 이소프로필기， 부틸기， 이소부틸기， t-부틸기 등)， 또는 탄소수 3 내지 20의 사이클로알킬기 (예를 들면， 사이클로프로필기， 사이클로부틸기， 사이클로핵실기 등) 등을 포함하는 탄소수 1 내지 20의 지방족 포화 탄화수소기 ; 탄소수 2 내지 10의 알케닐기 (예를 들면， 에테 닐기， 프로펜일기， 부테닐기 등)， 탄소수 2 내지 10의 알키닐기 (예를 들면， 에티닐기， 프로피닐기, 부티닐기 등)， 또는 탄소수 3 내지 20의 사이클로 알케닐기 등을 포함하는 탄소수 2 내지 20의 지방족 불포화 탄화수소기 ; 탄소수 6 내지 30의 아릴기 (예를 들면， 페닐기 등)를 포함하는 탄소수 6 내지 30의 방향족 탄화수소기; 히드록시기 ; 탄소수 1 내지 20의 알콕시기 (예를 들면， 메톡시기， 에특시기， 프로폭시기， t-부록시기 등); 에폭시기; 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 메틸기， 에틸기 등의 탄소수 1 내지 5의 알킬기임) 및 하기 화학식 2의 작용기로 이루어진 군 에서 선택되는 것일 수 있으며， 바람직하게는 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기， 및 하기 화학식 2의 작용기로 이루어진 군 에서 선택되는 것일 수 있다: 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 cycloalkenyl group of 20-20, etc .; Aromatic hydrocarbon groups having 6 to 30 carbon atoms including an aryl group having 6 to 30 carbon atoms (for example, a phenyl group); Hydroxyl group; An alkoxy group having 1 to 20 carbon atoms (eg, a methoxy group, a special group, a propoxy group, t-buroxy group, etc.); Epoxy groups; Amino group (-NR a R b , wherein R a and R b are each independently a methyl group, alkyl group having 1 to 5 carbon atoms such as ethyl group) and may be selected from the group consisting of functional groups of the formula (2), preferably It may be selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a functional group of the formula (2):
[화학식 2]  [Formula 2]
Figure imgf000018_0001
Figure imgf000018_0001
상기 화학식 2에서， b, c, T, X 및 Y는 앞서 정의한 바와 동일하다.  In Formula 2, b, c, T, X and Y are the same as defined above.
또， 상기 화학식 lb에서，  In addition, in the formula lb,
e, f 및 g는 각각 정수로서 0<e<100, l<f<5, 0<g<2이고， 그리고  e, f and g are each an integer of 0 <e <100, l <f <5, 0 <g <2, and
R은 각각 독립적으로 탄소수 1 내지 20의 알킬기 (예를 들면， 메틸기， 에틸기， 프로필기， 이소프로필기， 부틸기， 이소부틸기， t-부틸기 등)， 또는 탄소수 3 내지 20의 사이클로알킬기 (예를 들면， 사이클로프로필기 , 사이 클로부틸기， 사이클로핵실기 등) 등을 포함하는 탄소수 1 내지 20의 지방 족 포화 탄화수소기; 탄소수 2 내지 10의 알케닐기 (예를 들면， 에테닐기， 프로펜일기， 부테닐기 등)， 탄소수 2 내지 10의 알키닐기 (예를 들면， 에티 닐기， 프로피닐기， 부티닐기 등)， 또는 탄소수 3 내지 20의 사이클로알케 닐기 등을 포함하는 탄소수 2 내지 20의 지방족 불포화 탄화수소기; 탄소 수 6 내지 30의 아릴기 (예를 들면， 페닐기 등)을 포함하는 탄소수 6 내지 30의 방향족 탄화수소기 ; 히드록시기; 탄소수 1 내지 20의 알콕시기 (예를 들면， 메록시기, 에록시기， 프로폭시기， t-부특시기 등); 에폭시기; 아미노 기 (-NRR, 이때 R은 각각 독립적으로 메틸기， 에틸기 둥의 탄소수 1 내지 5의 알킬기이다); 및 이들의 조합으로 이루어진 군에서 선택되는 것이고， 바람직하게는 탄소수 1 내지 10의 알킬기， 탄소수 6 내지 18의 아릴기， 히드록시기, 에폭시기, 아미노기 및 이들의 조합으로 이루어진 군에.서 선 택되는 것일 수 있으며， 그리고 T는 *ᅳ (0) R (이때， R'은 탄소수 2 내지 10의 알케닐기일 수 있으며， 이중에서도 비닐기가 바람직하고 , ζ는 0 또는 1의 정수이다)이며， 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 hydrocarbon group containing a C6-C30 aryl group (for example, a phenyl group etc.); Hydroxyl group; An alkoxy group having 1 to 20 carbon atoms (for example, a hydroxy group, an hydroxy group, a propoxy group, a t-subspecific group, etc.); Epoxy groups; Amino groups (-NRR, wherein each R is independently a methyl group or an alkyl group having 1 to 5 carbon atoms in the ethyl column); And combinations thereof, preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxy group, an epoxy group, an amino group, and a combination thereof. T is * ᅳ ( 0 ) R (wherein R ′ may be an alkenyl group having 2 to 10 carbon atoms, among which a vinyl group is preferable, ζ is an integer of 0 or 1),
단， 상기 R과 Τ는 화학식 lc의 화합물 분자내 탄소수 2 내지 10의 알 케닐기， 바람직하게는 비닐기의 수가 3개 이상이 되도록 선택될 수 있다. 또， 상기 화학식 lc에서，  However, R and Τ 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. In addition, in Chemical Formula lc,
h, i 및 j는 각각 정수로서 0<h<100, l<i<5, 0<j<2이고， 그리고  h, i and j are each integers 0 <h <100, l <i <5, 0 <j <2, and
R 및 T는 상기 화학식 lb에서 정의한 바와 동일하다.  R and T are as defined in formula lb above.
또한 상기 성분 (a-1)의 제 1 유기 실리콘 화합물은 덴드리머 구조를 갖 는 것일 수 있으며， 이 경우 그 제너레이션수가 2 이하인 것이 바람직할 수 있다. 제너레이션수가 2를 초과하면 점도가 높아져 조성물로의 제어가 어려울 수 있으며， 합성단계가 늘어나 상업화가 어려울 수 있다.  In addition, 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.
보다 더 구체적으로 상기 성분 (a-1)의 제 1 유기 실리콘 화합물은 하기 화학식 3a 내지 3c의 화합물일 수 있다:  More specifically, the first organosilicon compound of component (a-1) may be a compound of formulas 3a to 3c:
[화학식 3a] Geiieiatioji 1
Figure imgf000020_0001
[Formula 3a] Geiieiatioji 1
Figure imgf000020_0001
[화학식 3b]  [Formula 3b]
Generation 1 Generation 1
Figure imgf000020_0002
Figure imgf000020_0002
[화학식 3c] [Formula 3c]
Figure imgf000020_0003
Figure imgf000020_0003
상기 화학식 3a 내지 3c에서 점선은 덴드리머 구조에서의 제너레이션 (generation)를 의미하며， 상기 식에서 m 및 n은 각각 In the formulas 3a to 3c, the dotted line represents a dendrimer structure. Means generation, in which m and n are each
독립적으로 0 내지 100의 정수이다. Independently an integer from 0 to 100.
(a-2) 제 2유기 실록산 화합물 (a-2) Second Organic Siloxane Compound
상기 제 2유기 실록산 화합물은 단위 분자 내 규소 (Si)를 포함하고， Q- 유 (quardri— function functional siloxane group: —0— (실록산결합)가 네개 결합된 Si원소), 또는 Q-유닛과 T-유닛 (Tri-functional siloxane group: -으 (실록산결합)가 세개 결합된 Si원소)의 흔합구조를 포함하며， 분자내에 Si에 직접 결합된 탄소수 2 내지 10의 알케닐기， 바람직하게는 비닐기를 3개 이상의 포함하는 유기 실톡산 화합물로서， 구체적으로는 하기 화학식 4의 구조를 갖는 것일 수 있다:  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 As an organosiloxane compound containing two or more, specifically, it may have a structure of the following general formula (4):
[화학식 4]  [Formula 4]
(R3Si)a(Si04/2)b(R2Si01/2)c(Si03/2)d(R3Si)e (R3Si) a (Si04 / 2 ) b (R2Si0 1/2) c (Si0 3/2) d (R3Si) e
상기 화학식 4에서，  In Chemical Formula 4,
a, b, c, d 및 e는 각각 정수로서， l<a<30, l<b<20, 0<c<30, 0<d<10 및 l≤e≤30이고， 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,
R은 각각 독립적으로 탄소수 1 내지 20의 알킬기 (예를 들면， 메틸기 에틸기， 프로필기， 이소프로필기， 부틸기， 이소부틸기， t-부틸기 등)， 또는 탄소수 3 내지 20의 사이클로알킬기 (예를 들면， 사이클로프로필기， 사이클로부틸기， 사이클로핵실기 등) 등 포함하는 탄소수 1 내지 20의 지방족 포화 탄화수소기; 탄소수 2 내지 10의 알케닐기 (예를 들면， 에테닐기， 프로펜일기， 부테닐기 등)， 탄소수 2 내지 10의 알키닐기 (예를 들면， 에티닐기， 프로피닐기， 부티닐기 등)， 또는 탄소수 3 내지 20의 사이클로알케닐기 등을 포함하는 탄소수 2 내지 20의 지방족 불포화 탄화수소기; 탄소수 6 내지 30의 아릴기 (예를 들면， 페닐기 등)을 포함하는 탄소수 6 내지 30의 방향족 탄화수소기; 히드록시기; 탄소수 1 내지 20의 알콕시기 (예를 들면, 메록시기， 에톡시기， 프로폭시기， t- 부록시기 등); 에폭시기; 아미노기 (-NRR, 이때 R은 각각 독립적으로 메틸기， 에틸기 등의 탄소수 1 내지 5의 알킬기임); 및 이들의 조합으로 이루어진 군에서 선택되며， 단 상기 R중 적어도 3개는 탄소수 2 내지 10의 알케닐기이며， 바람직하게는 상기 R은 모두 비닐기이다.  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 groups of 20 to 20; Aromatic hydrocarbon groups having 6 to 30 carbon atoms including an aryl group having 6 to 30 carbon atoms (for example, a phenyl group); Hydroxyl group; An alkoxy group having 1 to 20 carbon atoms (for example, a hydroxy group, an ethoxy group, a propoxy group, a t-addition group, etc.); Epoxy groups; Amino groups (-NRR, wherein R each independently represents an alkyl group having 1 to 5 carbon atoms such as a methyl group and an ethyl group); And combinations thereof, wherein at least three of R are alkenyl groups having 2 to 10 carbon atoms, and preferably all of R are vinyl groups.
또, 상기 제 2유기 실록산 화합물은 하기 화학식 5에서와 같이 분자내에 분지상 반복단위 (branched unit)로서 Q 유닛 (Si04/2), 또는 Q-유닛과 T— 유닛 종 3 내지 30개， 바람직하게는 3 내지 10개 포함하고， 터미널 유닛 (terminal unit)으로서 -SiR1!^2!^^이때， R1 및 R2는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고， R3은 탄소수 2 내지 10의 알케닐기， 바람직하게는 비닐기임)을 포함하는 3차원 망목 구조의 유기 실록산 화합물일 수 있다: In addition, 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.
[화학식 5]  [Formula 5]
Q유닛 또는 τ유닛의 분지상 반복단위가 더
Figure imgf000022_0001
More branched repeat units in Q or τ units
Figure imgf000022_0001
바람직하게는， 상기 제 2유기 실톡산 화합물은 하기 화학식 6a 내지 6c의 화합물로 이루어진 군에서 선택되는 것일 수 있다.  Preferably, the second organic siloxane compound may be selected from the group consisting of compounds represented by the following Chemical Formulas 6a to 6c.
[화학식 6a]  [Formula 6a]
Figure imgf000022_0002
Figure imgf000022_0002
(상기 화학식 6a에서, 1은 1 내지 30의 정수이며， 바람직하게는 1 내^ 10의 정수일 수 있다)  (In Formula 6a, 1 may be an integer of 1 to 30, preferably an integer of 1 to ^ 10)
[화학식 6b]
Figure imgf000023_0001
[Formula 6b]
Figure imgf000023_0001
화학삭 6  Chemical cutting 6
Figure imgf000023_0002
Figure imgf000023_0002
(상기 화학식 6c에서, m은 1 내지 10의 정수이고， n은 2 내지 30의 정수일 수 있다)  (In Chemical Formula 6c, m may be an integer of 1 to 10, n may be an integer of 2 to 30)
상기와 같은 구조를 갖는 제 2유기 실록산 화합물은 또한 25°C에서의 점도가 100 mPa . s 이상인 액상 또는 고체상인 것이 바람직할 수 있다. 이와 같은 점도특성을 갖기 때문에， 상기 제 2유기 실록산 화합물의 함량에 따라 점도조정 효과를 나타낼 수 있다. 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.
상기와 같은 (a-1)의 제 1 유기 실리콘 화합물 및 (a-2)의 제 2유기 실록산 화합물은 규칙성 고가지화 형태의 구조와 함께 분자내 3개 이상의 가교점을 갖기 때문에， 사슬을 우선 형성해야 하는 종래 실록산계 화합물과는 달리， 반웅성이 큰 말단형 가교제， 즉 수소원자로 말단처리된 유기 실록산 화합물 (H-terminated organosiloxane)을 통해 방향성 없이 반웅이 진행될 수 있어 경화시간이 짧고 가교도가 높다. 이에 따라 경화형 실리콘 조성물에 적용시 고온에서의 전단탄성률, 접착응력， 표면경화도 및 투명도가 향상되고， 장기간 자외선， 습기 및 열에 노출된 후에도 변색의 우려 없이 투명성을 유지할 수 있다. 또한， 이미 가교점이 형성되어 있는 상기 제 1 및 제 2유기 실록산 화합물을 짧은 가교제로 연결함으로써 고온 경화시에도 수축을 최소화 할 수 있다. 상기와 같은 제 1유기 실리콘 화합물 및 제 2유기 실록산 화합물은 상기 광디바이스용 경화형 투명 실리콘 조성물 내에 각각 단독으로， 또는 흔합하여 포함될 수 있다. 단독 사용시에 비해 흔합 사용시 제 1유기 실리콘 화합물에 의한 반웅속도 향상 효과와 제 2유기 실록산 화합물에 의한 물리적 특성의 향상을 동시에 나타낼 수 있다. 이에 따라 흔합되어 포함될 경우 그 흔합비는 특별히 한정되지 않으나， 본 발명의 효과에 대한 개선 정도 면에서 제 1 유기 실리콘 화합물과 제 2유기 실록산 화합물은 1:4 내지 1:8의 중량비로 흔합되어 포함되는 것이 바람직하고， 보다 바람직하게는 1:4 내지 1:5의 중량비로 흔합되어 포함될 수 있다. 만약 흔합비가 1:4 미만일 경우 조성물이 약하게 노란빛을 나타낼 수 있으며 열에도 쉽게 황변을 나타낼 수 있다. 또한 1:8을 초과할 경우 계 1 유기 실리콘 화합물의 효과가 미미할 수 있다. 성분 (b) Since the first organosilicon compound of (a-1) and the second organic siloxane compound of (a-2) as described above have a crosslinked point of 3 or more in the molecule together with a structure of a regular, highly branched form, the chain has priority. Unlike conventional siloxane compounds, which must be formed, 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. . Accordingly, when applied to the curable silicone composition, 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. In addition, by connecting 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. Accordingly, if included and mixed, 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. Component (b)
본 발명에 따른 광디바이스용 경화형 투명 실리콘 조성물은 상기 성분 Curable transparent silicone composition for an optical device according to the present invention is the component
(a)의 유기 실리콘 화합물 중의 알케닐기와 히드로실릴화 반웅에 의해 가교를 유도하여 조성물을 경화시키는 역할을 하는 성분 (b)으로서 가교제를 포함한다. 상기 가교제로는 통상 광디바이스용 경화용 투명 실리콘 조성물에서 사용되는 것이 사용될 수 있으나， 규소원자에 결합된 수소원자를 1분자 중에 2개 이상 포함하여 가교제뿐만 아니라， 투명 실리콘 조성물을 희석시켜 사용 용도에 알맞은 점도로 만드는 반웅성 희석제로도 작용할 수 있는 제 3유기 실록산 화합물이 바람직할 수 있다. 구체적으로， 상기 제 3유기 실록산 화합물은 하기 화학식 7의 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. Specifically, the third organic siloxane compound is represented by the formula
반복단위를 포함하며, 규소원자에 결합한 수소원자 (즉， SiH기)를 1 분자 중에 2개 이상, 바람직하게는 2 내지 50개 포함하는 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
오르가노히드로겐폴리실록산일 수 있다: Organohydrogenpolysiloxane can be:
[화학식 7]  [Formula 7]
-(R1pHqSiO(4-p.q)/2)- 상기 화학식 7에서， -(R 1pH q SiO (4-pq) / 2)-In Chemical Formula 7,
R1은 각각 독립적으로 치환되거나 또는 비치환된 탄소수 1 내지 20의 지방족 포화 탄화수소기 ; 치환되거나 또는 비치환된 탄소수 6 내지 30의 방향족 탄화수소기， 및 이들의 조합으로 이루어진 군에서 선택되는 것일 수 있고， 바람직하게는 치환되거나 비치환된 탄소수 1 내지 20의 알킬기, 치환되거나 비치환된 탄소수 3 내지 30의 사이클로알킬기， 치환되거나 비치환된 탄소수 6 내지 18의 아릴기 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 상기 R이 치환될 경우， 탄소수 1 내지 10의 알킬기， 할로겐기， 탄소수 1 내지 10의 할로알킬기， 히드록시기 및 시아노기로 이루어진 군에서 선택되는 작용기로 치환될 수 있다. R 1 each independently represent a substituted or unsubstituted aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms; A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and a combination thereof, preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, It may be selected from the group consisting of a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and a combination thereof. 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.
구체적으로 상기 R1은 메틸기， 에틸기， 프로필기， 이소프로필기， 부틸기, 이소부틸기， tert-부틸기， 펜틸기， 네오펜틸기， 핵실기， 헵틸기， 옥틸기， 노닐기， 데실기 등의 알킬기; 시클로핵실기 등의 시클로알킬기; 페닐기， 톨릴기， 크실릴기 및 나프틸기 등의 아릴기; 벤질기 및 페닐에틸기， 페닐프로필기 등의 아르알킬기 ; 이들 기의 수소 원자의 일부 또는 전부가 염소 원자, 불소 원자 및 브롬원자 등의 할로겐 원자로 치환된， Specifically, 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,
클로로메틸기， 3—클로로프로필기 및 3, 3, 3-트리플루오로프로필기 등의 할로겐화 알킬기 ; 또는 시아노기로 치환된 시아노에틸기 등을 들 수 있으며， 이중에서도 탄소수 1 내지 10의 알킬기가 바람직할 수 있고， 또 메틸기가 경화물의 내광성 및 내열성 면에서의 개선 효과가 우수하여 보다 더 바람직할 수 있다. 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.
또한， 상기 화학식 7의 오르가노히드로겐폴리실록산에 있어서， 전체 R1 중 적어도 0.01몰% 이상이 메틸기인 것이 성분 (a) 내지 성분 (c)와의 상용성이 우수하여， 백탁화되거나 조성물이 상분리될 우려가 없어 In addition, in 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
바람직하며， 보다 바람직하게는 0.05 내지 10몰%가 메틸기일 수 있다. 또한， 상기 p 및 q은 정수로서 0≤p≤4, 0≤q≤4이면서 0≤p+q<4이고， 바람직하게는 0≤p≤3, l≤q≤3이면서 l≤p+q≤3일 수 있다. Preferably, more preferably, 0.05 to 10 mol% may be a methyl group. In addition, 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.
상기 제 3유기 실록산 화합물에 있어서， 1개 분자 중에 2개 이상  In the third organic siloxane compound, two or more in one molecule
함유되는 규소 원자에 결합한 수소 원자 (즉， SiH기)는 분자쇄 말단 및 분자쇄 중간 중 어느 하나에 위치할 수도 있고 또는 둘 모두에 위치할 수도 있다. 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.
또한， 상기 제 3유기 실록산 화합물의 분자 구조는 직쇄상, 환상, 분지상 및 삼차원 망상 구조 중 어느 하나일 수 있지만， 1개 분자 중의 규소 원자의 수 (또는 중합도)는 1 내지 500개， 바람직하게는 3 내지 200개인 것이 좋다. 또한 상기 규소 원자에 결합한 수소 원자의 함유량은 상기 제 3유기 실록산 화합물 lg 당 0.1 내지 20 mmole/g의 범위인 것이 바람직하며， 1 내지 10 mmole/g의. 범위인 것이 보다 바람직하다.  In addition, 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. In addition, 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.
또한， 상기 제 3유기 실록산 화합물은 25°C에서의 l,000mPa . s 이하， 보다 바람직하게는 10 내지 lOOmPa · s의 점도를 갖는 것이 점도감소의 효과를 얻을 수 있어 좋다. In addition, 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.
상기 제 3유기 실록산 화합물의 구체예로는 1,1, 3,3-테트라메틸디실록산 1，3，5，7-테트라메틸시클로테트라실록산， 메틸히드로겐시클로폴리실록산， 메틸히드로겐실록산 · 디메틸실록산 환상 공중합체, 양쪽 말단  Specific examples of the third organic siloxane compound include 1,1,3,3-tetramethyldisiloxane 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrocyclocyclopolysiloxane, methylhydrogensiloxane and dimethylsiloxane Cyclic copolymer, both ends
트리메틸실록시기 봉쇄 메틸히드로젠폴리실록산, 양쪽 말단 Trimethylsiloxy group blockade methylhydrogenpolysiloxane, both ends
트리메틸실록시기 봉쇄 디메틸실톡산 · 메틸히드로젠실록산 공중합체， 양쪽 말단 디메틸히드로젠실록시기 봉쇄 디메틸폴리실록산， 양쪽 말단 디메틸히드로젠실록시기 봉쇄 디메틸살록산 · 메틸히드로젠실록산 공중합체， 양쪽 말단 트리메틸실록시기 봉쇄 Trimethylsiloxy group blocking dimethylsiloxane, methyl hydrogen siloxane copolymer, both terminal dimethyl hydrogen siloxy group blocking dimethyl polysiloxane, both terminal dimethyl hydrogen siloxy group blocking dimethyl saloxane, methyl hydrogen siloxane copolymer, both terminal trimethyl siloxy group blockade
메틸히드로젠실록산 · 디페닐실록산 공중합체， 양쪽 말단 Methylhydrogensiloxane diphenylsiloxane copolymer, both ends
트리메틸실록시기 봉쇄 메틸히드로젠실록산 · 디페닐실록산 · 디메틸실록산 공중합체， 양쪽 말단 트리 메틸실록시기 -봉쇄 Trimethylsiloxy group blockade Methylhydrogensiloxane, diphenylsiloxane, dimethylsiloxane copolymer, both terminal trimethylsiloxy group blockade
메틸히드로겐실록산 · 메틸페닐실록산 · 디메틸실록산 공중합체， 양쪽 말단 디메틸히드로겐실록시기 -봉쇄 Methylhydrogensiloxane, methylphenylsiloxane, dimethylsiloxane copolymer, both terminal dimethylhydrogensiloxy group -blocking
메틸히드로겐실록산 · 디메틸실록산 · 디페닐실록산공중합체， 양쪽 말단 디메틸히드로겐실록시기—봉쇄 Methylhydrogensiloxane · Dimethylsiloxane · Diphenylsiloxane Copolymer, Both Terminals Dimethylhydrogensiloxy Group—Sealed
메틸히드로겐실록산 · 디메틸실록산 · 메틸페닐실록산 공중합체， Methylhydrogensiloxane, dimethylsiloxane, methylphenylsiloxane copolymer,
(CH3)2HSi이 /2 단위와 Si04/2 단위로 이루어지는 공중합체， (CHs^HSiO^ 단위， (CH3)3Si01/2 단위 및 Si04/2 단위를 포함하는 공중합체， (CH 3) 2 HSi a / 2 units and Si0 4/2 units, copolymers consisting of, (CHs ^ ^ HSiO units, (CH 3) 3 Si0 1/2 units, and copolymer comprising Si0 4/2 units,
(CH3)2HSi01/2 단위와 Si04/2 단위와 (C6H5)Si03/2 단위로 이루어지는 공중합체 등을 들 수 있으며， 바람직하게는 하기 화학식 8a 내지 8d의 화합물 등을 들 수 있다: Copolymers of (CH 3 ) 2 HSi0 1/2 units, Si0 4/2 units, and (C 6 H 5 ) Si0 3/2 units, and the like. Can be mentioned:
[화학식 8a]  [Formula 8a]
Figure imgf000026_0001
Figure imgf000026_0001
[화학식 8b]  [Formula 8b]
Figure imgf000026_0002
W
Figure imgf000026_0002
W
25  25
[화학식 8c] [Formula 8c]
Figure imgf000027_0001
Figure imgf000027_0001
[화학식 8d]  [Formula 8d]
Figure imgf000027_0002
Figure imgf000027_0002
상기 화학식 8a 내지 8d에서， R1은 상기 화학식 7에서 정의한 바와 동일하고 , ν는 1 내지 20의 정수， w는 1 내지 100의 정수， X는 ◦ 내지 100의 정수， 그리고 y는 1 내지 50의 정수이다. In Formulas 8a to 8d, R 1 is the same as defined in Formula 7, ν 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.
이와 같은 제 3유기 실록산 화합물 중 1종 단독으로 이용하거나， 2종 이상을 혼합하여 사용할 수 있다.  One of these third organic siloxane compounds may be used alone, or two or more thereof may be mixed and used.
상기 성분 (b)는 성분 (a)의 유기 실리콘 화합물 중의 전체 규소 원자 또는 산소를 통해 규소원자에 결합한 알케닐기에 대하여， 상기 성분 (b) 중의 규소 원자에 결합한 수소 원자가 0.5 내지 3배 몰이 되는 양으로 포함되는 것이 바람직하다. 이와 같은 함량으로 포함될 때 보다 우수한 개선 효과를 나타낼 수 있다.  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.
또한， 상기 성분 (b)는 성분 (a)의 유기 실리콘 화합물 100 중량부에 대하여 1 내지 15 중량부로 포함되는 것이 바람직하다. 성분 (c)  In addition, the 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)
또， 본 발명에 따른 광디바이스용 경화형 투명 실리콘 조성물은 또한 상기 성분 (a) 증의 알케닐기와， 성분 (b)의 가교제 중의 SiH기와의  In addition, 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).
히드로실릴화 부가반웅을 진행 및 촉진시키기 위한 성분 (c)으로서 히드로실릴화 반응 촉매， 즉 부가 반응형 촉매를 포함할 수 있다. As component (c) for advancing and promoting the hydrosilylation addition reaction, a hydrosilylation reaction catalyst, ie, an addition reaction catalyst, may be included.
상기 부가 반웅형 촉매로서는 백금족 금속 촉매를 사용할 수 있으며， 그 구체적인 예로는 백금， 팔라듐 및 로듐 등의 백금족 금속; 염화백금산; 염화백금산과 1가 알코을과의 반웅물과 같은 알코올변성 염화 백금산; 염화백금산과 을레핀류， 비닐실록산 또는 아세틸렌 화합물과의 백금족 함유 배위 화합물; 테트라키스 (트리페닐포스핀)팔라듬 및 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
클로로트리스 (트리페닐포스핀) 로듐 등의 백금족 금속 화합물 등을 들 수 있다. Platinum group metal compounds such as chlorotris (triphenylphosphine) rhodium and the like.
상기한 부가 반응형 촉매 중 1종 단독으로 이용하거나, 또는 2종 이상을 흔합하여 사용할 수 있으며， 이중에서도 성분 (a) 및 (b)와의 상용성이 양호하고ᅳ 염소 불순물을 거의 함유하지 않는 염화 백금산을 실리콘 변성시킨 것이 바람직할 수 있다.  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.
또한, 상기 부가 반응형 촉매는 광디바이스용 경화형 투명 실리카 조성물 중에 촉매로서의 유효량으로 포함될 수 있으며， 바람직하게는 상기 성분 (a)의 유기 실리콘 화합물 총 중량에 대하여 백금족 금속 원소의 질량 환산으로 10 내지 5000ppm로 포함될 수 있으며， 50 내지 2000ppm의 함량으로 포함되는 것이 히드로실릴화 반웅을 보다  In addition, 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
효과적으로 촉진시킬 수 있어 보다 바람직하다. It is more preferable because it can be promoted effectively.
(d) 기타 첨가제 (d) other additives
본 발명에 따른 광디바이스용 경화형 투명 실리콘 조성물은 상기 성분 (a)와 함께 , 단위분자내 2개 이상의 규소원자에 결합된 알케닐기 또는 히드록시기를 포함하여 점도를 감소시키면서도 피착제와의 수소결합으로 접착증진 작용을 하고 경화 후 웅력을 완화시키는 작용을 하는  The curable transparent silicone composition for an optical device according to the present invention 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. To promote and relieve tension after hardening
점도조정용 실록산 화합물을 포함할 수 있다. It may include a siloxane compound for viscosity adjustment.
구체적으로 상기 점도 조정용 실록산 화합물은 주쇄가 하기 화학식 9로 표시되는 디오르가노실록산 (diorganosiloxane) 단위의 반복을 포함하고， 분자쇄 양쪽 말단이 트리오르가노실록시기 (triorganosiloxy group, (R3Si1/2))로 봉쇄되며， 단위 분자내 규소원자에 결합한 알케닐기 또는 히드록시기를 1개 분자 중에 2개 이상 포함하는 직쇄상， 분지상 또는 삼차원 망상 구조의 디오르가노폴리실록산일 수 있다: Specifically, 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:
[화학식 9]  [Formula 9]
-[R R2SiO2/2]- 상기 화학식 9에서, R1 및 R2는 각각 독립적으로 탄소수 2 내지 20의 알케닐기， 히드록시기， 탄소수 1 내지 20의 알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택된다. -[RR 2 SiO 2/2 ] -In Formula 9, 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.
바람직하게는 상기 점도조정용 실록산 화합물은 단위 분자 내에 규소 원자에 결합한 알케닐기 또는 히드록시기를 2 내지 10개, 보다 바람직하게는 2 내지 5개 포함할 수 있다. 이때 상기 알케닐기는 탄소수 2 내지 8의 알케닐기가 바람직하고， 보다 바람직하게는 탄소수 2 내지 6의 알케닐기일 수 있다. 그 구체예로는 비닐기， 알릴기， 이소프로페닐기 : 부테닐기， 펜테닐기， 핵세닐기 등을 들 수 있으며, 가장 바람직하게는 비닐기이다. Preferably, 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. At this time, 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.
상기 알케닐기 또는 히드록시기는 분자 중에서， 분자쇄 말단 및 분자쇄 비말단 (즉, 분자쇄 측쇄) 중 어느 하나에 존재할 수도 있고, 또는 둘 모두에 존재할 수도 있지만， 적어도 분자쇄 양쪽 말단에 존재하는 것이 바람직하다.  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.
또한， 상기 알케닐기 또는 히드록시기는 전체 유기기 중 0.01 내지 5.00mmole/g, 바람직하게는 0.10 내지 0.50mmole/g으로 포함되는 것이 좋다. 알케닐기 또는 히드록시기의 함량이 0.01mmole/g 미만인 경우 가교도가 떨어지고 접착력이 저하되어 바람직하지 않고， 5.00mmole/g 인 경우 부서지기 쉽거나 표면이 끈적한 특성이 나타날 수 있어 바람직하지 않다.  In addition, 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.
바람직하게는 상기 점도조정용 실록산 화합물은 하기 화학식 10a 내지 10g의 화합물로 이루어진 군에서 선택되는 것일 수 있다:  Preferably, the viscosity-adjusting siloxane compound may be selected from the group consisting of compounds of Formulas 10a to 10g:
(R4)2(R3)SiO[Si(R3)20]fSi(R3)(R4)2 (10a) (R 4 ) 2 (R 3 ) SiO [Si (R 3 ) 2 0] f Si (R 3 ) (R 4 ) 2 (10a)
(R4)3SiO[Si(R3)20]fSi(R4)3 (10b) (R 4 ) 3 SiO [Si (R 3 ) 20] fSi (R 4 ) 3 (10b)
(R4)2(R3)SiO[Si(R3)(R4)0]g[Si(R3)20]hSi(R3)(R4)2 (10c) (R 4 ) 2 (R 3 ) SiO [Si (R 3 ) (R 4 ) 0] g [Si (R 3 ) 2 0] h Si (R 3 ) (R 4 ) 2 (10c)
(R4)3SiO[Si(R3)(R4)0]g[Si(R3)20]hSi(R4)3 (lOd) (R 4 ) 3 SiO [Si (R 3 ) (R 4 ) 0] g [Si (R 3 ) 2 0] h Si (R 4 ) 3 (lOd)
(R3)3SiO[Si(R3)(R )0]g[Si(R3)20] hSi(R3)3 (lOe) (R 3 ) 3 SiO [Si (R 3 ) (R) 0] g [Si (R 3 ) 2 0] h Si (R 3 ) 3 (lOe)
(R4)(R3)2SiO[Si(R3)20]fSi(R3)2(R4) (lOf) (R 4 ) (R 3 ) 2 SiO [Si (R 3 ) 2 0] f Si (R 3 ) 2 (R 4 ) (lOf)
(R4)(R3)2SiO[Si(R3)(R4)0]g[Si(R3)20]hSi(R3)2(R4) (lOg) (R 4 ) (R 3 ) 2 SiO [Si (R 3 ) (R 4 ) 0] g [Si (R 3 ) 2 0] hSi (R 3 ) 2 (R 4 ) (lOg)
상기 화학식 10a 내지 lOg에서， R3 및 R4는 각각 독립적으로 탄소수 2 내지 20의 알케닐기, 히드록시기， 탄소수 1 내지 20의 알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되고， f는 0 내지 200， 바람직하게는 3 내지 120의 정수이고， g는 1 내지 10， 바람직하게는 1 내지 5의 정수이고， h는 0 내지 200, 바람직하게는 3 내지 110의 In 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
정수이다. Is an integer.
상기와 같은 점도조정용 실록산 화합물은 1종 단독으로 이용하거나， 2종 이상을 흔합하여 사용할 수 있다. 상기 점도조정용 실록산 화합물은 성분 (a)의 유기 실리콘 화합물 100중량부에 대하여 1 내지 30중량부로 포함되는 것이 물성저하의 우려없이 바람직한 점도감소 효과를 얻을 수 있어 좋으며， 바람직하게는 10 내지 20중량부로 포함될 수 있다. 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.
또한， 본 발명의 광디바이스용 경화형 투명 실리콘 조성물은  In addition, the curable transparent silicone composition for an optical device of the present invention
피착제와의 수소결합으로 접착증진 작용을 하는 알콕시기를 1개 이상 포함하는 실란 화합물을 포함할 수 있다. It may include a silane compound containing at least one alkoxy group which performs adhesion promoting action by hydrogen bonding with the adherend.
상기 실란 화합물은 하기 화학식 11의 화합물일 수 있다:  The silane compound may be a compound of Formula 11
[화학식 11]  [Formula 11]
(R60)z(R7) 2.Si-R8 (4.2.z.) (R 6 0) z (R 7) 2 .Si-R 8 (4. 2. Z.)
상기 화학식 11에서，  In Chemical Formula 11,
R6 및 R7은 각각 독립적으로 탄소수 1 내지 8의 지방족 R 6 and R 7 are each independently aliphatic having 1 to 8 carbon atoms
탄화수소기이고， Hydrocarbon group,
R8은 비닐기， 글리시딜기, 스티릴기， 메타크릴기， 아크릴기， 우레이도기 클로로알킬기， 메르캅토기， 이소시아네이트기， 아미노기， 디메틸아미노기， 이미다졸기 , 아세토아세테이트기 및 에폭시기로 이루어진 군에서 선택된 관능기로 치환된 탄소수 1 내지 8의 탄화수소기이며， 그리고 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 및 z'은 1<ζ<4, 0<∑'<3의 정수이면서， 1<ζ+ζ'<4이다.  z and z 'are integers of 1 <ζ <4, 0 <∑' <3 and 1 <ζ + ζ '<4.
구체적으로 상기 실란 화합물로는 트리에틸실리케이트,  Specifically, the silane compound may be triethyl silicate,
비닐트리에특시실란， 비닐트리메록시실란， 비닐트리아세록시실란， 비닐트리 (2-메록시에톡시 )실란， N-(3-아크릴록시 -2-히드록시프로필 )-3- 아미노프로필트리에록시실란， 3-메타크릴록시프로필트리메록시실란， 2ᅳ (3,4-에폭시사이클로핵실) 에틸트리메록시실란， N- 페닐아미노프로필트리메록시실란， N-(2-아미노에틸) -3- 아미노프로필메틸디메톡시실란， N-(2-아미노에틸) -3- 아미노프로필트리메톡시실란， N-(2-아미노에틸 )-3- 아미노프로필트리스 (2-에틸에록시 )실란， 3-아미노프로필트리에특시실란， 3ᅳ아미노프로필트리메톡시실란， 3-클로로프로필트리메톡시실란， 2-(3，4- 에폭시사이클로핵실)에틸트리메록시실란， (3- 글라이시독시프로필)메틸디에특시실란, 3ᅳ Vinyl triethylsilane, vinyltrimethoxysilane, vinyltriaceoxysilane, vinyltri (2-methoxyethoxy) silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2 '(3,4-epoxycyclonucleus) ethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (2-aminoethyl ) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltris (2-ethylethoxy) Silane, 3-aminopropyltrieoxysilane, 3 'aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2- (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane, (3- Glycidoxypropyl) methyldiecoxysilane, 3 ᅳ
글라이시독시프로필트리메톡시실란， 또는 비스 [3-Glycidoxypropyltrimethoxysilane, or bis [3-
(트리스에톡시실릴)프로필]테트라설파이드 등을 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상 흔합하여 사용할 수 있다. 상기와 같은 실란 화합물은 상기 성분 (a)의 유기 실리콘 화합물 (Trisethoxysilyl) propyl] tetrasulfide, etc. are mentioned, It can be used individually by 1 type or in mixture of 2 or more types. Such a silane compound is an organosilicon compound of the component (a)
100중량부에 대하여 0.1 내지 5중량부로 포함되는 것이 주요 구성성분과 분리되지 않으면서 접착력 증진효과를 얻을 수 있어 바람직하다. It is preferable to include 0.1 to 5 parts by weight with respect to 100 parts by weight to obtain an adhesion promoting effect without being separated from the main components.
상기한 성분들 외에도 본 발명에 따른 광디바이스용 경화형 투명 실리콘 조성물은 선택적으로 품드 실리카 등의 요변성 제어제; 결정성 실리카 등의 광 산란제; 실리카， 발연실리카 등의 보강재; 형광체; 석유계 용제 및 반웅성 관능기를 갖지 않는 비반응성 실리콘 오일 등의 점도 조정제; 탄소-관능성 (carbon-functional) 실란， 에폭시기， 알콕시기， 규소 원자에 결합한 수소 원자 (즉, SiH기) 및 규소 원자에 결합한 비닐기 등의 알케닐기 중 1종 이상을 갖는， 상기 (a) 성분 이외의 실리콘 화합물 등의 접착성 향상제; 은 및 금 등의 금속 분말을 포함하는 도전성 부여제: 코발트 블루 등의 무기 안료; 유기 염료 등의 착색제; 산화 세륨, 탄산 아연， 탄산 망간， 적산화철， 산화 티탄， 카본 블랙 등의 내열성 및 난연성 향상제; 3-메틸 -1-부틴 -3-을， 3，5-디메틸 1-핵실ᅳ 3-올， 페닐부티놀， 1，3，5，7-테트라메틸— 1,3,5,7-테트라비닐시클로테트라실톡산， 1，3—디비닐- 테트라메틸디실록산， 테트라메틸테트라비닐테트라시클로실록산，  In addition to the above components, the curable transparent silicone composition for an optical device according to the present invention 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-butyn-3-, 3,5-dimethyl 1-nuxyl 3-ol, phenylbutynol, 1,3,5,7-tetramethyl— 1,3,5,7-tetravinyl Cyclotetrasiloxane, 1,2-divinyl-tetramethyldisiloxane, tetramethyltetravinyltetracyclosiloxane,
벤조트리아졸， 포스핀 화합물， 머캅토 화합물 등의 반웅 억제제; 또는 파장 조정제 등의 첨가제를 더 포함할 수 있다. Reaction inhibitors such as benzotriazole, phosphine compound and mercapto compound; Or an additive such as a wavelength regulator.
상기 첨가제는 본 발명의 효과를 저해하지 않는 범위내에서 용도에 따라 적절한 함량으로 사용될 수 있다.  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.
상기와 같은 조성을 갖는 본 발명에 따른 광디바이스용 경화형 투명 실리콘 조성물은， 조성물내 알케닐기 이외의 규소 원자에 결합한 전체 1가 탄화수소기의 80몰% 이상， 바람직하게는 90 내지 100몰%가  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
메틸기인 것이 내열성 및 내광성 (내자외선성)이 우수하며 , 열 및 자외선 등의 스트레스에 의한 변색을 포함한 열화에 대한 내성이 우수하여 보다 바람직하다. 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.
이와 같이 본 발명의 광디바이스용 경화형 투명 실리콘 조성물은 성분 (a) 내지 (c)와 선택적으로 성분 (e)의 기타 첨가제를 흔합하여 제조할 수도 있고， 성분 (a) 및 (b)를 포함하는 부분과 성분 (b)를 제외한 (a) 내지 (c) 및 선택적으로 성분 (d)를 포함하는 부분을 각각 별도로 제조한 후， 이들 두 부분을 흔합하여 제조할 수도 있다.  Thus, 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.
본 발명의 광디바이스용 경화형 투명 실리콘 조성물은 상기 성분 (a)의 유리 실리콘 화합물을 주재로 포함하고, 또 반웅성이 큰 상기 성분 (b)의 말단형 가교제를 통해 방향성 없이 반응 진행함으로써， 종래의 긴 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,
경화시간을 요구하지 않으며 강한 기계적 물성， 낮은 선팽창계수 및 높은 접착력을 나타낸다. 그 결과， 접착응력 및 표면 경화도가 높아 광반도체용 접착제로서 적합하고， 소자로부터의 광 추출효율을 높이기 위한 투명 소재로서의 기능을 동시에 나타내며, 장기간 자외선， 습기 및 열의 노출 후에도 그 투명성이 유지되고 변색이 일어나지 않는 특성을 갖는다. It does not require hardening time and shows strong mechanical properties, low coefficient of linear expansion and high adhesion. As a result, it is suitable as an adhesive for optical semiconductors due to its high adhesive stress and surface curing degree, and simultaneously exhibits a function as a transparent material for improving light extraction efficiency from the device, and its transparency is maintained even after exposure to ultraviolet rays, moisture and heat for a long time. It does not happen.
또한， 상기 광디바이스용 경화형 투명 실리콘 조성물의 경화는 통상의 경화 조건으로 행할 수 있으며， 예를 들면 100 내지 18CTC에서 30분 내지 3시간 동안 가열함으로써 행할 수 있다. 특히， 조성물을 경화시켜 얻어지는 경화물의 쇼어 (Shore) D 경도는 35 이상， 특히 45 이상인 것이 바람직하며， 상기 쇼어 D 경도를 45 이상으로 만들기 위한 경화 조건은 통상적으로， 본 발명의 조성물을 100 내지 18C C에서 30분 내지 3시간의 조건으로 가열하여 경화시킴으로써 얻을 수 있다.  In addition, 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. In particular, 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 | curing on C conditions for 30 minutes-3 hours.
발명의 실시를 위한 형태  Embodiment for Invention
이하， 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.  Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
[합성예 1] 화학식 la 화합물의 합성  Synthesis Example 1 Synthesis of Chemical Formula la Compound
환류응축기， 교반기， 온도계， 질소주입기를 포함하는 부가깔때기가 장착된 4구 500ml 반응조에， 메틸트리스디메틸실록시실란 13.5g과， 크실렌에 50ppm으로 희석되어 있는 0가형 백금촉매 0.02g을 투입하고 5CTC에서 가열 교반하였다. 결과의 반웅 흔합물에 비닐  Into a four-necked 500 ml reactor equipped with an addition funnel containing a reflux condenser, a stirrer, a thermometer, and a nitrogen injector, 13.5 g of methyltrisdimethylsiloxysilane and 0.02 g of a zero-valent platinum catalyst diluted to 50 ppm were added to 5CTC. Was stirred under heating. Vinyl to the reaction mixture of results
트리스트리메틸실록시실란 48.4g을 부가깔때기를 이용하여 1시간 동안에 걸쳐 서서히 적가하고, 24시간 더 반웅시킨 후 감압 농축하였다. 결과로 수득한 투명한 옅은 갈색의 액체를 다시 4구 반웅조에 투입하고， 를루엔 무수화물 200ml와 수산화바륨 촉매 O.Olg을 넣고 80°C에서 가열 48.4 g of tristrimethylsiloxysilane was slowly added dropwise over an hour using an addition funnel, further stirred for 24 hours, and then concentrated under reduced pressure. The resultant transparent pale brown liquid was again added to a four-necked semi-aperture, and 200 ml of toluene anhydride and O.Olg of a barium hydroxide catalyst were heated at 80 ° C.
교반하였다. 결과의 반웅물에， 마이크로시브를 이용하여 함유하고 있는 수분을 사전에 제거한 알릴알코올 29g(0.5mole(excess))을 부가깔때기를 이용하여 한시간에 걸쳐 투입한 후 세시간 더 반웅시켰다. 반웅완료 후 페이퍼필터를 이용하여 촉매를 제거하고， 증류수 /를루엔 1:1 흔합액 Stirred. In the resulting reaction product, 29 g (0.5 mole (excess)) of allyl alcohol from which water was previously removed using microsieve was added over an hour using an addition funnel, followed by further reaction for three hours. After the reaction was completed, the catalyst was removed using a paper filter, and distilled water / luene 1: 1 mixture was used.
200g을 넣고 10분간 교반한 뒤 유기층을 분리하였다. 분리된 유기층을 다량의 증류수로 반복 세척하고 감압 증류하여 생성물 (la)를 수득하였다. W 200 g was added thereto, stirred for 10 minutes, and the organic layer was separated. The separated organic layer was washed repeatedly with a large amount of distilled water and distilled under reduced pressure to give the product (la). W
31 결과의 생성물은 크실렌 30g에 용해시켜 보관하였다.  31 The resulting product was stored dissolved in 30 g of xylene.
Figure imgf000033_0001
Figure imgf000033_0001
(1a)  (1a)
(상기 반웅식에서， R은 -CH3이다) [합성예 2] 화학식 lb 화합물의 합성 (In the above reaction formula, R is -CH 3. ) Synthesis Example 2 Synthesis of the compound lb
환류웅축기， 교반기， 온도계， 질소주입기를 포함하는 부가깔때기가 장착된 4구 500ml 반옹조에， 를루엔 무수물 120ml,  In a four-necked 500 ml reaction tank equipped with an addition funnel containing a reflux condenser, a stirrer, a thermometer and a nitrogen injector, 120 ml of toluene anhydride,
폴리메틸하이드로젠실록산 (SiH 7.8mmole/g, GELEST) 20g, 그리고 0가 백금촉매 O.Olg을 투입하고 5( C까지 가열 교반하였다. 결과의 반응 흔합물에 부가깔대기를 이용하여 비닐트리메톡시실란 22.3g올 두시간에 걸쳐 서서히 적가하고， 24시간 더 반웅시켰다. 결과의 반웅물을 에탄을을 이용하여 수차례 세척한 후， 감압증류하여 ^은 황색의 액체를 20 g of polymethylhydrogensiloxane (SiH 7.8mmole / g, GELEST) and 0-valent platinum catalyst O.Olg were added and stirred by heating to 5 (C. The resultant reaction mixture was added with vinyltrimethoxy using an addition funnel. 22.3 g of silane was slowly added dropwise over two hours, and further reacted for 24 hours.The resulting reaction product was washed several times with ethane and distilled under reduced pressure to obtain a yellowish liquid.
수득하였다. 수득된 ^은 황색의 액체를 다시 4구 반응조에 투입하고， 틀루엔 무수화물 200ml와 수산화바륨 촉매 O.Olg을 넣고 80°C로 가열 교반하였다. 결과의 반웅물에， 마이크로시브를 이용하여 함유하고 있는 수분을 사전에 제거한 알릴알코올 29g(0.5mole(excess))을 부가깔때기를 이용하여 한시간에 걸쳐 투입한 후 세시간 더 반응시켰다. 반응완료 후 페이퍼필터를 이용하여 촉매를 제거하고 증류수 /를루엔 1:1 흔합액 Obtained. The obtained yellow liquid was added to a four-necked reaction tank again, 200 ml of toluene anhydride and O.Olg barium hydroxide catalyst were added thereto, and the mixture was heated and stirred at 80 ° C. Contained with microsieve in the resulting reaction water 29 g (0.5 mole (excess)) of allyl alcohol from which water was removed in advance was added over an hour using an addition funnel, followed by further reaction for three hours. After completion of the reaction, the catalyst was removed using a paper filter and distilled water / luene 1: 1 mixture was used.
200g을 넣고 10분간 교반한 뒤 유기층을 분리하였다. 분리된 유기층을 다량의 증류수로 반 세척하고 감압 증류하여 생성물 (lb)를 수득하였다. 결과의 생성물은 크실렌 30g에 용해시켜 보관하였다. 200 g was added thereto, stirred for 10 minutes, and the organic layer was separated. The separated organic layer was washed half with a large amount of distilled water and distilled under reduced pressure to give the product (lb). The resulting product was dissolved in 30 g of xylene and stored.
Figure imgf000034_0001
Figure imgf000034_0001
(1b)  (1b)
(n의 평균 값 = 50) [합성예 3] 화학식 lc 화합물의 합성  (Average value of n = 50) Synthesis Example 3 Synthesis of Compound lc
환류웅축기， 교반기， 온도계， 질소주입기를 포함하는 부가깔때기가 장착된 4구 500ml 반응조에, 를루엔 무수물 120ml와  In a four-necked 500 ml reactor equipped with an addition funnel containing a reflux condenser, agitator, thermometer, and nitrogen injector, 120 ml of toluene anhydride and
폴리디메틸디하이드로젠실록산 (SiH 7.0mmole/g, GELEST) 20g, 그리고 20 g of polydimethyldihydrogensiloxane (SiH 7.0mmole / g, GELEST), and
0가 백금촉매 O.Olg을 투입하고 50°C까지 가열 교반하였다. 결과의 반웅 흔합물에 부가깔대기를 이용하여 비닐트리메톡시실란 22.3g을 두시간에 걸쳐 서서히 적가하고， 24시간 더 반웅시켰다. 결과의 반웅물을 에탄을을 이용하여 수차례 세척한 후 감압증류하여 넓은 황색의 액체를 수득하였다. 수득된 ^은 황색의 액체를 다시 4구 반응조에 투입하고， 를루엔 0-valent platinum catalyst O.Olg was added and stirred with heating to 50 ° C. To the resulting reaction mixture, 22.3 g of vinyltrimethoxysilane was slowly added dropwise over two hours using an addition funnel, and the reaction was further stirred for 24 hours. The resulting reaction product was washed several times with ethane and distilled under reduced pressure to give a wide yellow liquid. ^ Obtained yellow liquid was added to a four-necked reactor again, and toluene
무수화물 200ml와 수산화바륨 촉매 O.Olg을 넣고 8CTC로 가열 Add 200ml of anhydride and O.Olg barium hydroxide catalyst and heat it to 8CTC
교반하였다. 결과의 반웅물에， 마이크로시브를 이용하여 함유하고 있는 수분을 사전에 제거한 알릴알코올 29g(0.5mole(excess))을 부가깔때기를 이용하여 한시간에 걸쳐 투입한 후， 세시간 더 반웅시켰다. 반웅완료 후 페이퍼필터를 이용하여 촉매를 제거하고 증류수 /를루엔 1:1 흔합액 Stirred. In the resulting reaction water, add 29 g (0.5 mole (excess)) of allyl alcohol from which water was previously removed using a microsieve. After an hour of use, the reaction was repeated for three hours. After the reaction was completed, the catalyst was removed using a paper filter and distilled water / luene 1: 1 mixture was used.
200g을 넣고 10분간 교반한 뒤 유기층을 분리하였다. 분리된 유기층을 다량의 증류수로 반복 세척하고 감압 증류하여 생성물 (lc)를 수득하였다 결과의 생성물은 크실렌 30g에 용해시켜 보관하였다. 200 g was added thereto, stirred for 10 minutes, and the organic layer was separated. The separated organic layer was washed repeatedly with a large amount of distilled water and distilled under reduced pressure to obtain the product (lc). The resulting product was dissolved in 30 g of xylene and stored.
Figure imgf000035_0001
Figure imgf000035_0001
(1c)  (1c)
(n의 평균 값 = 50)  (average of n = 50)
[합성예 4] 화학식 5의 화합물 합성 Synthesis Example 4 Synthesis of Compound of Chemical Formula 5
4구 500ml 반응조에 테트라에톡시실란 20.8g(0.1mole, Sigma- Aldrich) 및 에탄을 100ml을 투입하고 실온에서 두시간 동안 강하게 교반하였다. 반응조의 온도를 0°C로 낮춘 후 디메틸비닐클로로실란 100 ml of 20.8 g (0.1 mole, Sigma-Aldrich) and ethane tetraethoxysilane were added to a four-neck 500 ml reactor, and the mixture was stirred vigorously at room temperature for two hours. After lowering the temperature of the reactor to 0 ° C, dimethylvinylchlorosilane
71g(0.3mole(excess), Dow chemical사제)을 한시간에 걸쳐 투입하고， 두시간 더 반응시켰다. 반웅완료 후 결과의 반응물에 71 g (0.3 mole (excess), Dow Chemical Co., Ltd.) was added over an hour and reacted for another two hours. After reaction, the resultant reactant
증류수 /디에틸에테르 1:1 흔합액 100g과 탄산수소나트륨 수용액을 넣고 10분간 교반한 후， 유기층을 분리하였다. 분리된 유기층을 다량의 증류수로 반복 세척하고 감압 증류하여， 분자내 Q 유닛의 분지상 반복단위를 평균 4.2개 포함하고， 터미널 유닛으로서 -Sil^RSR^이때， R 및 R2는 각각 메틸기이고， R3은 비닐기임)을 포함하는 3차원 망목구조의 생성물 (5) 48g을 수득하였다. 수득된 생성물은 크실렌 30g에 용해시켜 보관하였다.
Figure imgf000036_0001
100 g of distilled water / diethyl ether 1: 1 mixed solution and an aqueous sodium hydrogen carbonate solution were added thereto, stirred for 10 minutes, and the organic layer was separated. The separated organic layer was repeatedly washed with a large amount of distilled water and distilled under reduced pressure, containing an average of 4.2 branched repeat units of the Q unit in the molecule, -Sil ^ RSR ^ as a terminal unit, wherein R and R 2 are each methyl groups, R 3 is a vinyl group) to give 48 g of a three-dimensional network product (5). The product obtained was dissolved in 30 g of xylene and stored.
Figure imgf000036_0001
(5)  (5)
상기 제조된 화합물 (5)에서의 Q-유닛 (quardri-function)의 수는 평균 4.2이었다. [합성예 5] 화학식 6c의 화합물 합성  The number of Q-units (quardri-function) in the compound (5) prepared above was 4.2. Synthesis Example 5 Compound Synthesis of Chemical Formula 6c
4구 500ml 반응조에 테트라에톡시실란 20.8g(0.1mole, Sigma—  20.8 g (0.1 mole, Sigma— of tetraethoxysilane in a 4-neck 500 ml reactor
Aldrich), 1，3，5，7—테트라비닐테트라메틸사이를로테트라실록산 Aldrich), 1,3,5,7—tetravinyltetramethylcylotetrasiloxane
69.0g(0.2mole, GELEST) 및 에탄올 200ml를 투입하고, 촉매로 69.0g (0.2mole, GELEST) and 200ml of ethanol were added, and as a catalyst
트리플로로메탄술포닉산 0.35g을 투입한 후 실온에서 두시간 동안 반웅시켰다. 결과의 반웅물에 증류수 /에탄을 4:1 흔합액을 10분에 걸쳐 첨가한 후 한시간 동안 더 반웅시키고， 이후， 비닐디메틸에특시실란 130.3g (l.Omole(excess), Dow chemical)을 한시간에 걸쳐 투입하고 두시간 더 반웅시켰다. 결과로 수득된 반응물에 증류수 /디에틸에테르 1:1 흔합액 100g과 탄산수소나트륨 수용액을 넣고 10분간 교반한 뒤 0.35 g of trichloromethanesulphonic acid was added thereto, followed by reaction at room temperature for 2 hours. Distilled water / ethane was added to the resulting reaction product over 10 minutes after adding a 4: 1 mixture over 10 minutes, and then 130.3 g (l.Omole (excess), Dow chemical) of vinyl dimethyl was added. Injected over an hour and reacted for another two hours. 100 g of distilled water / diethyl ether 1: 1 mixed solution and an aqueous sodium hydrogen carbonate solution were added to the resulting reaction mixture, which was then stirred for 10 minutes.
유기층을 분리하였다. 분리된 유기층을 다량와 증류수로 반복 세척하고 감압 증류하여 최종 생성물 (6c) 131g을 수득하였다. 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).
Figure imgf000037_0001
Figure imgf000037_0001
(6c)  (6c)
상기에서 제조된 화합물 (6c)에서 m 및 n은 각각 1 내지 5， 및 4 내지 16이며， 평균 3.5 및 8.0이었다. 시험예 1  In compound (6c) prepared above, m and n were 1 to 5, and 4 to 16, respectively, with an average of 3.5 and 8.0. Test Example 1
1. 분자량 측정  1. Molecular weight measurement
상기 합성예 1 내지 5에서 제조한 화합물의 중량평균분자량 (Mw), 수평균분자량 (Mn) 및 분자량 분포 (PDI)을 GPC를 이용하여 측정하고 이를 수율과 하기 표 1에 나타내었다.  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.
[표 1]  TABLE 1
Figure imgf000037_0002
Figure imgf000037_0002
2. 비닐함량 분석 2. Vinyl Content Analysis
상기 합성예 1 내지 5에서 제조한 화합물의 FT-IR을 이용하여 분자 자체의 Si-ᄋ back bone 기준 피크 (Internal standard peak) 대비 상대적 비닐 피크값을 측정하고， 이를 통해 화합물내 비닐함량을 추정하였다. 상기에서 사용된 계산식은 하기 수학식 1에서와 같이 비닐함량을 알고 있는 표준시료 5종의 FT-IR 결과에서 주쇄 특성피크 높이와 C = C 특성피크 높이와의 비율 대비 비닐함량과의 관계식을 통해 도출되었다. 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. . The equation used above is based on the relationship between the vinyl content versus the ratio of the main chain characteristic peak height and the C = C characteristic peak height in the FT-IR results of five standard samples with known vinyl contents, as shown in Equation 1 below. Derived.
[수학식 1]  [Equation 1]
Y = 0.5779X - 0.1331  Y = 0.5779 X-0.1331
상기 수학식 1에서，  In Equation 1,
Y = 비닐함량 (vinyl content, mmole/g),  Y = vinyl content (vinyl content, mmole / g),
X = Hvinyl/H siloxane  X = Hvinyl / H siloxane
Hvinyi = 비닐 흡수 피크의 높이 (height of vinyl absorbance peak, @ 1600-165ᄋ cm— 1〉 Hvinyi = height of vinyl absorbance peak (@ 1600-165 ᄋ cm— 1 〉
Hsnoxane = Si ◦ 백본 흡수 피크의 높이 (height of Si_0 backbone absorbance peak, @ 1940cm—1) H snoxane = Si ◦ height of Si_0 backbone absorbance peak, @ 1940 cm— 1
보정상수 (Calibration constant, M) = 0.5779, 그리고  Calibration constant (M) = 0.5779, and
인터셉트 (Intercept, N) = -0.1331이다.  Intercept (N) = -0.1331.
그 결과를 하기 도 1 내지 5， 및 표 2에 나타내었다.  The results are shown in FIGS. 1 to 5 and Table 2 below.
[표 2]  TABLE 2
Figure imgf000038_0001
도 4에서 합성예 4의 화합물은 2140nm에서 약하게 피크가 나타났다. 이는 합성예 4에서 제조된 화합물 분자내 SiH 결합이 잔류하기 때문인 것으로 생각되며， 이 같은 SiH 결합으로 인한 입체 장애에 의해 반웅성 o 저하된 것으로 추정된다.
Figure imgf000038_0001
In FIG. 4, 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.
[합성예 6] 화학식 8a의 화합물 합성 Synthesis Example 6 Synthesis of Compound of Chemical Formula 8a
환류응축기， 교반기， 온도계， 및 질소주입기를 포함하는 부가깔때기가 구비된 4구 250ml 반응조에， 테트라메틸디실록산 13.2g(0.1mole, Additional funnels, including reflux condensers, stirrers, thermometers, and nitrogen injectors, In a four-neck 250 ml reactor equipped with 13.2 g (0.1 mole, tetramethyldisiloxane,
Wacker) 및 데카메틸사이클로펜틸실록산 37. lg(0.1mole, Sigma- - Aldrich)을 투입하고 4CTC까지 가열하였다. 결과의 흔합 반웅물에 Wacker) and decamethylcyclopentylsiloxane 37. lg (0.1 mole, Sigma--Aldrich) was added and heated to 4CTC. In the mixed reaction of the result
촉매로서 트리플로로메탄술포닉산 0.05g을 투입한 후 40°C에서 두시간 동안 강하게 교반하고, 증류수 /에탄올 4:1 흔합액을 10분에 걸쳐 After adding 0.05 g of trichloromethanesulphonic acid as a catalyst, the mixture was stirred vigorously at 40 ° C. for 2 hours, and distilled water / ethanol 4: 1 mixture was mixed over 10 minutes.
첨가하여 한시간 동안 더 반응시켰다. 반응완료 후 결과로 수득된 The reaction was further added for one hour. After completion of reaction
반응물에 증류수 /디에틸에테르 1:1 흔합액 100g과 탄산수소나트륨 100 g of distilled water / diethyl ether 1: 1 mixture and sodium hydrogencarbonate
수용액을 넣고 10분간 교반한 뒤 유기층을 분리하였다. 결과로 분리된 유기층을 다량의 증류수로 반복 세척한 후 감압 증류하여 최종 After adding the aqueous solution and stirring for 10 minutes, the organic layer was separated. The resultant organic layer was washed repeatedly with a large amount of distilled water and then distilled under reduced pressure.
생성물 (8a) 28g을 수득하였다. 28 g of product (8a) were obtained.
Figure imgf000039_0001
Figure imgf000039_0001
(상기 식에서, R1은 각각 메틸기이고， V는 4이다) (Wherein R 1 is a methyl group and V is 4)
[합성예 7] 화학식 8b의 화합물 합성 Synthesis Example 7 Compound of Chemical Formula 8b
환류웅축기， 교반기， 온도계， 및 질소주입기를 포함하는 부가깔때기가 구비된 4구 250ml 반웅조에， 1，3，5，7—테트라메틸사이클로테트라실록산 24.0g(0.1mole, GELEST) 및 1，1，3，3—테트라메틸디실록산 13.2g(0. lmole, Wacker)을 투입하고 40°C까지 가열하였다. 결과의 흔합 반응물에 4, 250 ml semi-aperture with addition funnel containing reflux condenser, stirrer, thermometer, and nitrogen injector, 1,3,5,7—tetramethylcyclotetrasiloxane 24.0 g (0.1 mole, GELEST) and 1,1 , 3,3-tetramethyldisiloxane 13.2g (0.lmole, Wacker) was added and heated to 40 ° C. To a mixed reactant of the result
촉매로서 트리플로로메탄술포닉산 0.05g을 투입한 후 4( C에서 두시간 동안 강하게 교반하고， 이후 증류수 /에탄올 4:1 흔합액을 10분에 걸쳐 첨가하여 한시간 동안 더 반웅시켰다. 결과로 수득된 반웅물에 대한 처리는 상기 합성예 1에서와 동일한 방법으로 실시하여 최종생성물 (8b) 24.5g을 수득하였다. 0.05 g of trichloromethanesulphonic acid was added as a catalyst, followed by vigorous stirring at 4 (C for two hours, and then distilled water / ethanol 4: 1 mixture was added over 10 minutes to further react for one hour. The reaction was carried out in the same manner as in Synthesis Example 1 to obtain 24.5 g of the final product (8b).
Figure imgf000039_0002
Figure imgf000039_0002
[합성예 8] 화학식 8c 화합물의 합성 환류웅축기， 교반기， 온도계， 및 질소주입기를 포함하는 부가깔때기가 구비된 4구 1,000ml 반응조에， 1,3，5，7-테트라메틸사이클로테트라실톡산 240.5g(1.0mole, GELEST) 및 핵사메틸디실록산 3.3g(0.02mole, Wacker)을 투입하고 40°C까지 가열하였다. 결과의 흔합 반응물에 촉매로서 트리플로로메탄술포닉산 0.35g을 투입한 후 40°C에서 두시간 동안 강하게 교반하고， 다시 증류수 /에탄올 4:1 흔합액을 10분에 걸쳐 첨가한 후 세시간 동안 더 반응시켰다. 결과로 수득된 반응물에 대한 처리는 상기 합성예 1에서와 동일한 방법으로 실시하여 최종생성물 (8c) 212. Og을 수득하였다. 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).
Figure imgf000040_0001
(8c)
Figure imgf000040_0001
(8c)
(상기 식에서 R1은 각각 메틸기이고, w는 45이다.) [합성예 9] 화학식 8d 화합물의 합성 (Wherein R 1 is a methyl group and w is 45.) Synthesis Example 9 Synthesis of Compound 8d
환류웅축기， 교반기， 온도계， 및 질소주입기를 포함하는 부가깔때기가 구비된 4구 500ml 반웅조에， 1，3，5，7-테트라메틸사이클로테트라실록산 240g(1.0mole, GELEST), 1，1，3，3-테트라메틸디실록산 26.4g(0.2mole, Wacker) 및 테트라에톡시실란 20.8g(0.1mole, Sigma-Aldrich)을 투입하고 40°C까지 가열하였다. 결과의 흔합 반응물에 촉매로서 트리플로로메탄술포닉산 0.35g을 투입한 후 4CTC에서 두시간 동안 강하게 교반하고， 이후 증류수 /에탄올 4:1 흔합액을 15분에 걸쳐 첨가한 후 세시간 동안 더 반웅시켰다. 결과로 수득된 반응물에 대한 처리는 상기 합성예 1에서와 동일한 방법으로 실시하여 최종생성물 (8d)을 수득하였다.
Figure imgf000041_0001
240 g (1.0mole, GELEST), 1,1, 240 g (1,3,5,7-tetramethylcyclotetrasiloxane) in a four-neck 500 ml semi-aperture equipped with an addition funnel containing a reflux condenser, agitator, thermometer, and nitrogen injector. 26.4 g (0.2 mole, Wacker) of 3,3-tetramethyldisiloxane and 20.8 g (0.1 mole, Sigma-Aldrich) of tetraethoxysilane were added and heated to 40 ° C. 0.35 g of trichloromethanesulphonic acid as a catalyst was added to the resultant reaction mixture, followed by vigorous stirring at 4CTC for 2 hours, and then distilled water / ethanol 4: 1 mixture was added over 15 minutes, followed by further reaction for 3 hours. Treatment of the resulting reaction product was carried out in the same manner as in Synthesis Example 1 to obtain a final product (8d).
Figure imgf000041_0001
(상기 식에서， R1은 각각 메틸기이고， X는 40， 그리고 y는 1이다.) 시험예 2 (In the above formula, each R 1 is a methyl group, X is 40, and y is 1).
상기 합성예 7 내지 10에서의 합성 결과를 증명하기 위하여， 점도 및 경도를 각각 측정하고， 그 결과를 하기 표 3에 나타내었다.  In order to prove the synthesis results in Synthesis Examples 7 to 10, the viscosity and hardness were measured, respectively, and the results are shown in Table 3 below.
이때， 상기 점도는 브룩필드 콘앤플레이트 타입 점도계 (Brookfield HBDV-II pro, CP5D* 이용하여 측정하였다.  In this case, the viscosity was measured using a Brookfield Corn and Plate Type Viscometer (Brookfield HBDV-II pro, CP5D *).
또， 상기 경도는 표준 레진을 이용하여 측정하였으며， 상세하게는 폴리디메틸실록산 (PDMS, 점도 10,000cP, 비닐함량 0.3mmole/g) 96 중량부， 합성 화합물 3중량부， 디메틸말레이트 0.5 중량부， 부가반웅형 백금촉매 0.5 중량부를 흔합 및 탈포하여 15C C에서 두시간 경화시킨 후 측정하였다.  In addition, 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.
[표 3]  TABLE 3
Figure imgf000041_0002
Figure imgf000041_0002
[실시예 1 내지 21] 광디바이스용 경화형 투명 실리콘 조성물의 제조 먼저, 상기 합성예 1 내지 5에서 제조한 크실렌 함유 유리 실리콘 화합물을 각각 비닐실록산 수지 (VSIOOO™, Hanse Chemie사제; [Examples 1 to 21] Preparation of Curable Transparent Silicone Compositions for Optical Devices First, the xylene-containing glass silicone compounds prepared in Synthesis Examples 1 to 5 were each manufactured from vinylsiloxane resins (VSIOOO ™, manufactured by Hanse Chemie;
비닐함량 0.12mmole/g)와 하기 표 4에 기재된 다양한 흔합비로 흔합한 후 감압 증류하여 흔합 수지 1 내지 21을 제조하였다. 이때 상기 비닐실록산 수지를 100중량부로 사용한 것을 비교수지로 하였다.  0.12 mmole / g of vinyl content) and various mixing ratios shown in Table 4 below, followed by distillation under reduced pressure, to prepare the mixed resins 1 to 21. At this time, 100 parts by weight of the vinylsiloxane resin was used as a comparative resin.
[표 4] TABLE 4
Figure imgf000041_0003
Figure imgf000041_0003
Figure imgf000042_0001
상기 표 4를 통해 제조된 흔합수지 1 내지 21을 각각 주요수지로 하고， 또 상기 합성예 6 내지 9에서 합성된 화합물 중 경도가 가장 높은
Figure imgf000042_0001
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.
합성예 9의 화합물을 주요 가교제로 하여， 하기 표 5에 제시된 성분 및 함량으로 흔합하여 광디바이스용 경화형 투명 실리콘 조성물을  Using the compound of Synthesis Example 9 as a main crosslinking agent, it was mixed with the ingredients and contents shown in Table 5 below to obtain a curable transparent silicone composition for an optical device.
제조하였다.  Prepared.
[표 5]
Figure imgf000042_0002
TABLE 5
Figure imgf000042_0002
Figure imgf000043_0001
상기 가교제 factor는 1.5로 하였으며， 이는 비닐함량대비 SiH 함량의 비율에 대해 첨가한 비닐레진 양으로 필요한 가교제 양을 구하고 이에 1.5를 곱하여 첨가하였다.
Figure imgf000043_0001
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.
[비교예 1] 광디바이스용 경화형 투명 실리콘 조성물의 제조 Comparative Example 1 Preparation of Curable Transparent Silicone Composition for an Optical Device
주요수지로 VS10000™(HanseChemie, Vinyl 0.05mmole/g) 100중량부， 가교제로 합성예 9의 화합물 factor 1.5에 해당하는 중량부, 중합억제제로 메틸부틴올 (Sigma-Aldrich) 0.3중량부， 부가반웅형 백금촉매 (NC25 As the main resin, 100 parts by weight of VS10000 ™ (HanseChemie, Vinyl 0.05mmole / g), as a crosslinking agent, and a part by weight of compound factor 1.5 of Synthesis Example 9 as a polymerization inhibitor 0.3 parts by weight of methylbutynol (Sigma-Aldrich), addition catalyst for platinum (NC25)
CATALYST, DOW CORNING TORAY) 0.5중량부， 그리고 CATALYST, DOW CORNING TORAY) 0.5 parts by weight, and
비닐트리에록시실란 0.5중량부를 흔합， 탈포하여 광디바이스용 경화형 투명 실리콘 조성물을 제조하였다. 0.5 parts by weight of vinyltriethoxysilane was mixed and degassed to prepare a curable transparent silicone composition for an optical device.
[비교예 2] 광디바이스용 경화형 투명 실리콘 조성물의 제조 Comparative Example 2 Preparation of Curable Transparent Silicone Composition for an Optical Device
주요수지로 VQM803TM(HanseChemie, Vinyl 0.21mmole/g) 100증량부， 가교제로 합성예 9의 화합물 factor 1.5에 해당하는 중량부， 중합억제제로 메틸부틴올 (Sigma-Aldrich사제) 0.3중량부， 부가반응형 백금촉매 (NC25™ CATALYST, DOW CORNING TORAY사제) 0.5중량부， 그리고 100 parts by weight of 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 ™ Catalyss, manufactured by Dow Corning Toray), and
비닐트리에록시실란 0.5중량부를 흔합，탈포하여 광디바이스용 경화형 투명 실리콘 조성물을 제조하였다. 0.5 parts by weight of vinyltriethoxysilane was mixed and degassed to prepare a curable transparent silicone composition for an optical device.
상기 비교예 2에서 사용된 VQM803™ (HanseChemie, Vinyl  VQM803 ™ (HanseChemie, Vinyl) used in Comparative Example 2
0.21mmole/g)는 Q-유닛 (quardri-function)을 포함하는 실리콘 수지로 Qᅳ유닛을 일부 포함하는 합성예 1 및 2의 생성물과 비교 가능하여 비교예로 선정하였다. 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.
[시험예 3] 광디바이스용 경화형 투명 실리콘 조성물의 평가 [Test Example 3] Evaluation of the Curable Transparent Silicone Composition for an Optical Device
상기 실시예 1~21， 및 비교예 1, 2에서 제조한 광디바이스용 경화형 투명 실리콘 조성물에 대하여 경화조건에 따라 경화한 후 경화속도， 광투과도， 특성을 분석하였다.  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.
1) 경화속도  1) Curing Speed
시차주사열량분석기 (DSC)를 이용하여 승온조건에서의 반웅형태와 고정온도에서의 반웅속도를 평가하였으며， 그 중 고정온도에서의  Differential Scanning Calorimetry (DSC) was used to evaluate reaction form at elevated temperature and reaction rate at fixed temperature, among which
반웅속도를 통하여 각 물질에 따른 경화속도를 비교하였다. Through the reaction rate, the curing rate of each material was compared.
고정온도는 일반적인 경화조건인 15CTC로 설정하였고， 열량변화가 더 이상 일어나지 않는 지점을 경화완료지점으로 하였다. 그 결과를 도 6에 나타내었다.  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.
도 6에 나타난 바와 같이， 선형 고분자만으로 이루어진 비교예 1의 광디바이스용 경화형 투명 실리콘 조성물에 비해 망상구조의 고분자를 포함하는 비교예 2의 광디바이스용 경화형 투명 실리콘 조성물의  As shown in FIG. 6, 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
경화속도가 더 빠른 것으로 나타났다. 이와 마찬가지로 합성예 1 내지 6에서 제조한 고분지화된 실리콘 화합물을 포함하는 실시예 1 내지 21의 광디바이스용 경화형 투명 실리콘 조성물은 비교예 2에 비해 현저히 증가된 경화속도를 나타내었으며, 규칙성 고가지화 수지의 함량이 높아질수록 경화속도 또한 빨라지는 것을 확인하였다. 2) 광투과도 The cure rate was shown to be faster. Similarly Examples 1 to 21 containing the highly branched silicone compound prepared in Synthesis Examples 1 to 6 Curable transparent silicone composition for an optical device showed a significantly increased curing rate compared to Comparative Example 2, it was confirmed that the higher the content of the regular high branching resin, the faster the curing rate. 2) Light transmittance
상기 실시예 1~21 및 비교예 1, 2에서 제조한 광디바이스용 경화형 투명 실리콘 조성물을 유리 위에 두께 1mm 및 2mm로 각각 도포한 후 15CTC에서 두시간 경화시켰다. 결과의 경화막에 대해 UV-VIS  The 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
분광기 (spectrometer)를 이용하여 유리 광투과도 대비 450nm 및 450 nm vs. glass light transmittance using a spectrometer
600nm에서의 광투과도를 측정하였다. 이때， 400nm에서의 광투과도는 투명성을 보기 위함이고, 600nm에서의 광투과도는 황변정도를 보기 위함이다. 그 결과를 하기 도 7에 나타내었다. 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.
도 7은 실시예 1 내지 21 및 비교예 1,2의 광디바이스용 경화형 투명 실리콘 조성물을 두께 1mm로 도포하고 경화시킨 후， 광투과도 (%)를 측정한 결과를 나타낸 그래프이다.  7 is a graph showing the results of measuring the light transmittance (%) after coating and curing the curable transparent silicone composition for optical devices of Examples 1 to 21 and Comparative Examples 1 and 2 with a thickness of 1 mm.
도 7에 나타난 바와 같이， 고가지화 실록산 화합물의 첨가시 그 함량에 상관없이 광투과도가 향상되었다. 특히 실시예 9 내지 10의 경우 가장 높은 광투과도 향상을 보였다. 한편， 합성예 5의 경우 함량을 증가시켜도 합성예 4까지의 광투과율까지는 못미치나， 실시예 13 내지 21에 사용된 흔합수지 증 합성예 5의 수지도 합성예 1내지 4를 소량 흔용 첨가함에 따라 합성예 5을 사용한 흔합수지와 유사한 광투과도 향상효과를 나타내었다.  As shown in FIG. 7, the light transmittance was improved regardless of the content of the highly branched siloxane compound. In particular, Examples 9 to 10 showed the highest light transmittance improvement. On the other hand, in the case of Synthesis Example 5, 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.
3) 전단탄성률 (Shear Modulus) 3) Shear Modulus
상기 2) 광투과율에서와 동일한 방법으로 실시하되 유리가 아닌 알루미늄 컵에 2mm 두께로 도포하고 후 150°C에서 두시간 경화시켜 각 실시예 및 비교예의 경화시편을 제조하고, DMA(Dynamic Mechanical Analaysis, MettlerToledo) 장비를 이용하여 전단웅력상에서의 2) The same method as in the light transmittance, but was applied to an aluminum cup, not glass, 2mm thickness and then cured at 150 ° C. for 2 hours to prepare hardened specimens of each Example and Comparative Example, DMA (Dynamic Mechanical Analaysis, Mettler Toledo) On the shear force
저장탄성률을 측정하였다. 이때， 실시예 1~21 중 각 흔합수지에 대해 대표할만한 실시예들을 선정하고 그 결과를 도 8에 나타내었다. Storage modulus was measured. In this case, among the examples 1 to 21, representative examples for each of the mixed resins were selected, and the results are shown in FIG. 8.
도 8에 나타난 바와 같이， 고가지화 실톡산 화합물을 포함하는 실시예 10， 13, 15 및 20의 조성물이 비교예 1 및 2에 비해 높은 전단탄성률을 나타내었으며， 특히 실시예 10의 경우 유리전이온도를 기점으로 완만한 변화를 보여 이상적인 탄성률 특성을 가짐을 확인할 수 있다. 또한 고가지화 실록산 화합물의 함량이 높은 실시예 10 및 실시예 20의 경우 고온에서도 수십 MPa의 전단탄성률을 유지하였다. 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.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개 량 형태 또한 본 발명의 권리범위에 속하는 것이다.  Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvement forms of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.
산업상 이용가능성 Industrial availability
본 발명에 따른 광디바이스용 접착성 투명 조성물은， 경화시간이 짧고， 고온에서의 높은 전단탄성률， 높은 가교도， 접착웅력， 표면 경화도 및 투 명도를 나타내며， 장기간 자외선， 습기 및 열에 노출된 후에도 변색의 우 려 없이 투명성을 유지할 수 있어 광반도체용 접착제 또는 투명 소재로서 유용하다.  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.

Claims

청구범위 [청구항 1] 유기 실리콘 화합물， 가교제， 및 부가반응형 촉매를 포함하며， 리콘 조성물. [청구항 2] 제 1항에 있어서， 상기 유기 실리콘 화합물이 하기 (a— 1)의 제 1 유기 실리콘 화합물, (a- 2)의 제 2유기 실록산 화합물 및 이들의 흔합물로 이루어진 군에서 선택되 는 것인 광디바이스용 경화형 투명 실리콘 조성물: Claims Claim 1 An organic silicone compound, a crosslinking agent, and an addition reaction type catalyst. 2. The compound according to claim 1, wherein the organosilicon compound is selected from the group consisting of the first organosilicon compound of (a-1), the second organic siloxane compound of (a-2), and a mixture thereof. Curable transparent silicone composition for an optical device:
(a-1) 하기 화학식 la 내지 lc의 화합물로 이루어진 군에서 선택되는 제 1 유기 실리콘 화합물; 그리고  (a-1) a first organosilicon compound selected from the group consisting of compounds of the formula la to lc; And
(a-2) 단위 분자 내 규소를 포함하고, Q-유닛 (quardri-function functional siloxane group), 또는 Q-유닛과 T一유닛 (Tri— functional siloxane group)의 흔합구조를 포함하며， 분자내에 Si에 직접 결합된 탄 소수 2 내지 10의 알케닐기를 3개 이상의 포함하는 하기 화학식 4의 제 2 유기 실록산 화합물.  (a-2) containing silicon in a unit molecule, including a Q-unit (quardri-function functional siloxane group) or a mixed structure of Q-unit and T-unit (Tri-functional siloxane group), A second organosiloxane compound of formula (4) comprising three or more alkenyl groups having 2 to 10 carbon atoms directly bonded to it.
[화학식 la] [Formula la]
Figure imgf000047_0002
(상기 화학식 la에서，
Figure imgf000047_0002
(In the above formula la,
a, b 및 c는 각각 정수로서， 0≤a≤3, 0<b≤3, 0≤c≤3이고， z  a, b and c are each an integer, 0≤a≤3, 0 <b≤3, 0≤c≤3, z
Figure imgf000048_0001
조합으로 이루어진 군에서 선택되며 (이때, R은 각각 독립적으로 탄소수 1 내지 20 의 지방족 포화 탄화수소기， 탄소수 2 내지 20의 지방족 불포화 탄화수소 기， 탄소수 6 내지 30의 방향족 탄화수소기， 히드록시기， 탄소수 1 내지 20의 알콕시기， 에폭시기， 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립 적으로 탄소수 1 내지 5의 알킬기이다) 및 이들의 조합으로 이루어진 군 에서 선택된다)， 그리고
Figure imgf000048_0001
And each R is independently an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a hydroxyl group, and 1 to 20 carbon atoms. An alkoxy group, an epoxy group, an amino group (-NR a R b , wherein R a and R b are each independently selected from the group consisting of 1 to 5 carbon atoms) and combinations thereof, and
Y 및 Z는 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소 기， 탄소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 히드록시기， 에폭시기, 아미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알킬기이다) 및 하기 화학식 2 의 작용기로 이루어진 군에서 선택된다: Y and Z are 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 hydroxyl group, 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 functional group of formula (2):
[화학식 2]  [Formula 2]
Figure imgf000048_0002
Figure imgf000048_0002
상기 화학식 2에서, b, c, T, X 및 Y는 앞서 정의한 바와 동일하다) [화학식 lb]
Figure imgf000049_0001
In Formula 2, b, c, T, X and Y are the same as defined above) [Formula lb]
Figure imgf000049_0001
(상기 화학식 lb에서，  (In the formula lb,
e, f 및 g는 각각 정수로서 0≤e≤100, l≤f≤5, 0≤g<2이고， 덴드리머 구조로 표현시 제너레이션 (generation) 수가 2 이하이며，  e, f and g are each an integer of 0≤e≤100, l≤f≤5, 0≤g <2, and the generation number when expressed in a dendrimer structure is 2 or less,
R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄 소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향 족 탄화수소기， 히드록시기， 탄소수 1 내지 20의 알콕시기， 에폭시기， 아 미노기 (― NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알 킬기이다) 및 이들의 조합으로 이루어진 군에서 선택되고， 그리고 R is each independently an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, and an amino group. 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
T는
Figure imgf000049_0002
(이때， R'은 탄소수 2 내지 10의 알케닐기이고， z는 ◦ 또 는 1의 정수이다)이며， T
Figure imgf000049_0002
(Wherein R 'is an alkenyl group having 2 to 10 carbon atoms, z is an integer of ◦ or 1),
단, 상기 R과 T는 화학식 lb의 화합물 분자내 탄소수 2 내지 10의 알 케닐기의 수가 3개 이상이 되도록 선택된다)  Wherein R and T 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)
[화학식 lc]  [Formula lc]
Figure imgf000049_0003
Figure imgf000049_0003
(상기 화학식 lc에서， h, i 및 j는 각각 정수로서 0<h<100, l<i<5, 0<j<2이고， (In Chemical Formula lc, h, i and j are integers, respectively, 0 <h <100, l <i <5, 0 <j <2,
R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄 소수 2 내지 20의 지방족 불포화 탄화수소기， 탄소수 6 내지 30의 방향 족 탄화수소기， 히드록시기， 탄소수 1 내지 20의 알콕시기, 에폭시기， 아 미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알 킬기이다) 및 이들의 조합으로 이루어진 군에서 선택되고, 그리고 R is each independently an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, and an amino group. A 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
T는 飞 ^ (이때， R'은 탄소수 2 내지 10의 알케닐기이고， z는 0 또 는 1의 정수이다)이며， T is 飞 ^ (where R 'is an alkenyl group having 2 to 10 carbon atoms and z is an integer of 0 or 1),
단, 상기 R과 T는 화학식 lc의 화합물 분자내 탄소수 2 내지 10의 알 케닐기의 수가 3개 이상이 되도록 선택된다)  Provided that R and T 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)
[화학식 4]  [Formula 4]
(R3Si)a(Si04/2)b(R2Si01/2)c(Si03/2)d(R3Si)e (R3Si) a (Si04 / 2 ) b (R2Si0 1/2) c (Si0 3/2) d (R3Si) e
(상기 화학식 4에서，  (In Formula 4,
a, b, c, d 및 e는 각각 정수로서, l<a<30, l<b<20, 0<c<30, 0<d<10 및 l<e<30이고， 그리고  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
R은 각각 독립적으로 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄 소수 2 내지 20의 지방족 불포화 탄화수소기, 탄소수 6 내지 30의 방향 족 탄화수소기， 히드록시기， 탄소수 1 내지 20의 알콕시기， 에폭시기, 아 미노기 (-NRaRb, 이때 Ra 및 Rb는 각각 독립적으로 탄소수 1 내지 5의 알 킬기이다) 및 이들의 조합으로 이루어진 군에서 선택되며， 단， 상기 R중 적어도 3개는 탄소수 2 내지 10의 알케닐기이다) R is each independently an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, and an amino group. 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 2 to 10 alkenyl)
[청구항 3]  [Claim 3]
제 2항에 있어서，  The method of claim 2,
상기 제 1 유기 실리콘 화합물이 하기 화학식 3a 내지 3c의 화합물로 이루어진 군에서 선택되는 것인 광디바이스용 경화형 투명 실리콘 조성물.  Curable transparent silicone composition for an optical device, wherein the first organic silicon compound is selected from the group consisting of compounds represented by the following Chemical Formulas 3a to 3c.
[화학식 3a]
Figure imgf000051_0001
[Formula 3a]
Figure imgf000051_0001
(상기 화학식 3b 및 3c에서， m 및 n은 각각 독립적으로 0 내지 100의 정수이다)  (In the formulas 3b and 3c, m and n are each independently an integer of 0 to 100)
[청구항 4]  [Claim 4]
제 2항에 있어서， The method of claim 2 ,
상기 제 2유기 실록산 화합물이 분자내에 Q-유닛 (Si04/2), 또는 Q- 유닛과 T-유닛 (Si03/2)을 포함하는 분지상 반복단위 (branched unit)를 3 내지 30개 포함하고， 터미널 유닛 (terminal unit)으로서 — SH^R2!^^아때， R1 및 R2는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고， R3은 탄소수 2 내지 10의 알케닐기이다)을 포함하는 삼차원 망목구조의 유기 실록산 화합물인 광디바이스용 경화형 투명 실리콘 조성물. The second organic siloxane compound may comprise a branched repeating unit comprising 3 Q-units (Si0 4/2 ) or Q-units and T-units (Si0 3/2 ) in the molecule. 30 to 30, and as a terminal unit (SH ^ R 2 ! ^ ^ As time, 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) A curable transparent silicone composition for an optical device, which is an organic siloxane compound having a three-dimensional network structure.
[청구항 5]  [Claim 5]
제 2항에 있어서，  The method of claim 2,
상기 제 2유기 실록산 화합물이 하기 화학식 6a 내지 6c의 화합물로 이루어진 군에서 선택되는 것인 광디바이스용 경화형 투명 실리콘 조성물.  Curable transparent silicone composition for an optical device, wherein the second organic siloxane compound is selected from the group consisting of compounds represented by the following Chemical Formulas 6a to 6c.
[화학식 6a]  [Formula 6a]
Figure imgf000052_0001
Figure imgf000052_0001
(상기 화학식 6a에서， 1은 1 내지 30의 정수이다)  (In Formula 6a, 1 is an integer of 1 to 30)
[화학식 6b]  [Formula 6b]
Figure imgf000052_0002
Figure imgf000052_0002
[화학식 6c]
Figure imgf000053_0001
[Formula 6c]
Figure imgf000053_0001
(상기 화학식 6c에서， m은 1 내지 10의 정수이고， n은 2 내지 30의 정수이다)  (In Chemical Formula 6c, m is an integer of 1 to 10, n is an integer of 2 to 30)
[청구항 6]  [Claim 6]
제 2항에 있어서，  The method of claim 2,
상기 제 2유기 실록산 화합물이 25°C에서의 점도가 lOOmPa · s 이상의 액상 또는 고체상인 것인 광디바이스용 경화형 투명 실리콘 조성물. Curable transparent silicone composition for an optical device, wherein the second organic siloxane compound is a liquid or solid phase having a viscosity at 25 ° C. of 100 mPa · s or more.
[청구항 7]  [Claim 7]
제 1항에 있어서，  The method of claim 1,
상기 가교제가 하기 화학식 7의 반복단위를 포함하며， 규소원자에 결합한 수소원자를 1분자 중에 2개 이상 포함하는 제 3유기 실록산 화합물인 것인 광디바이스용 경화형 투명 실리콘 조성물:  The curable transparent silicone composition for an optical device, wherein the crosslinking agent is a third organic siloxane compound including a repeating unit represented by the following Chemical Formula 7 and containing at least two hydrogen atoms bonded to silicon atoms in one molecule:
[화학식 7]  [Formula 7]
-(R1 pHqSiO(4-p-q)/2)- 상기 화학식 7에서， -(R1 pH q SiO (4-pq) / 2)-In Chemical Formula 7,
p 및 q은 정수로서 0<p<4, 0<q<4이면서 0<p+q<4이고， 그리고  p and q are integers 0 <p <4, 0 <q <4 and 0 <p + q <4, and
R1은 각각 독립적으로 탄소수 1 내지 10의 알킬기， 할로겐기， 탄소수 1 내지 10의 할로알킬기， 히드록시기 및 시아노기로 이루어진 군에서 선택되는 치환기로 치환되거나 또는 비치환된， 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 및 이들의 조합으로 이루어진 군에서 선택되는 것이다. 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 It is selected from the group consisting of a hydrocarbon group, an aromatic hydrocarbon group of 6 to 30 carbon atoms, and a combination thereof.
[청구항 8]  [Claim 8]
제 1항에 있어서，  The method of claim 1,
상기 가교제가 하기 화학식 8a 내지 8d의 화합물로 이루어진 군에서 선택되는 것인 광디바이스용 경화형 투명 실리콘 조성물:  Curable transparent silicone composition for an optical device, wherein the crosslinking agent is selected from the group consisting of the compounds of formulas 8a to 8d:
[화학식 8a]
Figure imgf000054_0001
[Formula 8a]
Figure imgf000054_0001
[화학식 8d] [Formula 8d]
Figure imgf000054_0002
Figure imgf000054_0002
상기 화학식 8a 내지 8d에서，  In Chemical Formulas 8a to 8d,
R1은 각각 독립적으로 탄소수 1 내지 10의 알킬기， 할로겐기， 탄소수 내지 10의 할로알킬기， 히드록시기 및 시아노기로 이루어진 군에서 선택되는 치환기로 치환되거나 또는 비치환된， 탄소수 1 내지 20의 지방족 포화 탄화수소기， 탄소수 6 내지 30의 방향족 탄화수소기， 및 이들의 조합으로 이루어진 군에서 선택되는 것이고， Each R 1 is independently an aliphatic saturated hydrocarbon of 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; Group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a combination thereof;
V는 1 내지 20의 정수, w는 1 내지 100의 정수， X는 ᄋ 내지 100의 정수， 그리고 y는 1 내지 50의 정수이다.  V is an integer from 1 to 20, w is an integer from 1 to 100, X is an integer from 0 to 100, and y is an integer from 1 to 50.
[청구항 9]  [Claim 9]
제 1항에 있어서，  The method of claim 1,
상기 가교제가 25°C에서의 점도가 l,000mPa · s 이하인 것인 광디바이스용 경화형 투명 실리콘 조성물. The crosslinking agent is a viscosity at 25 ° C is less than l, 000 mPa · s Curable transparent silicone composition for an optical device.
[청구항 10]  [Claim 10]
제 1항에 있어서，  The method of claim 1,
상기 가교제가， 가교제 분자 중 규소 원자에 결합한 수소원자가 상기 유기 실리콘 화합물 중의 전체 규소 원자에 결합한 알케닐기에 대하여 To the alkenyl group in which the crosslinking agent is bonded to all silicon atoms in the organosilicon compound by a hydrogen atom bonded to a silicon atom in the crosslinker molecule.
0.5 내지 3배 몰이 되는 양으로 포함되는 것인 광디바이스용 경화형 투명 실리콘 조성물. Curable transparent silicone composition for an optical device that is contained in an amount of 0.5 to 3 times molar.
[청구항 11]  [Claim 11]
제 1항에 있어서, /  The method of claim 1, wherein
상기 가교제가 상기 유기 실리콘 화합물 100 중량부에 대하여 1 내지 15중량부로 포함되는 것인 광디바이스용 경화형 투명 실리콘 조성물.  Curable transparent silicone composition for an optical device, wherein the crosslinking agent is contained in 1 to 15 parts by weight based on 100 parts by weight of the organosilicon compound.
[청구항 12]  [Claim 12]
제 1항에 있어서，  The method of claim 1,
상기 부가 반웅형 촉매가 백금족 금속 촉매인 광디바이스용 경화형 투명 실리콘 조성물.  The curable transparent silicone composition for an optical device, wherein the addition semi-aromatic catalyst is a platinum group metal catalyst.
[청구항 13]  [Claim 13]
제 1항에 있어서，  The method of claim 1,
상기 부가 반웅형 촉매가 유기 실리콘 화합물 총 중량에 대하여 백금족 금속 원소의 질량 환산으로 10 내지 5000ppm의 양으로 포함되는 광디바이스용 경화형 투명 실리콘 조성물.  The curable transparent silicone composition for an optical device, wherein the addition semi-amorphous catalyst is 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.
[청구항 14]  [Claim 14]
제 1항에 있어서，  The method of claim 1,
상기 광디바이스용 경화형 투명 실리콘 조성물을 유리 위에 두께 1mm 내지 2mm로 도포 후 경화시 유리 광투과도 대비 450nm 및 600nm에서 90% 이상의 광투과도를 나타내는 광디바이스용 경화형 투명 실리콘 조성물.  A curable transparent silicone composition for optical devices, wherein the curable transparent silicone composition for optical devices has a thickness of 1 mm to 2 mm on glass and then exhibits a light transmittance of 90% or more at 450 nm and 600 nm compared to glass light transmittance when cured.
[청구항 15]  [Claim 15]
제 1항에 있어서，  The method of claim 1,
상기 광디바이스용 경화형 투명 실리콘 조성물을 두께 2mm로 경화시 전단탄성를이 25°C에서 150Mpa 이하이고， 10CTC 이상의 온도에서 Shear elasticity when curing the curable transparent silicone composition for optical devices to a thickness of 2mm is less than 150Mpa at 25 ° C, at a temperature of 10CTC or more
20Mpa 이상인 광디바이스용 경화형 투명 실리콘 조성물. Curable transparent silicone composition for optical devices of 20 Mpa or more.
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