[go: up one dir, main page]

WO2015079677A1 - Matériau optique - Google Patents

Matériau optique Download PDF

Info

Publication number
WO2015079677A1
WO2015079677A1 PCT/JP2014/005888 JP2014005888W WO2015079677A1 WO 2015079677 A1 WO2015079677 A1 WO 2015079677A1 JP 2014005888 W JP2014005888 W JP 2014005888W WO 2015079677 A1 WO2015079677 A1 WO 2015079677A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
optical material
material according
functional group
curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/005888
Other languages
English (en)
Japanese (ja)
Inventor
和彦 兒島
大川　直
晴彦 古川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Toray Specialty Materials KK
Original Assignee
Dow Corning Toray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Co Ltd filed Critical Dow Corning Toray Co Ltd
Priority to JP2015550562A priority Critical patent/JP6427107B2/ja
Publication of WO2015079677A1 publication Critical patent/WO2015079677A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties

Definitions

  • the present invention relates to an optical material having excellent gas barrier properties and heat resistance.
  • Curable polyorganosiloxane is used as a protective agent for a semiconductor element and a sealing agent for an optical semiconductor in an optical semiconductor device such as a photocoupler, a light emitting diode, and a solid-state imaging element (Patent Documents 1 and 2).
  • the curable polyorganosiloxane is excellent in light resistance, heat discoloration, and impact resistance, but has high gas permeability.
  • a light emitting device such as a light emitting diode
  • the light extraction efficiency is improved by providing a light reflecting film made of silver or a silver alloy.
  • silver and silver alloys are chemically very unstable. Therefore, when it reacts with oxygen, moisture, hydrogen sulfide, sulfurous acid gas, etc. in the air, silver oxide or silver sulfide is generated and the surface turns brown or black, lowering the luminance and reducing the reliability of the semiconductor device.
  • polyorganosiloxanes phenyl silicone compositions are said to have lower gas permeability than methyl silicone compositions, but this is not sufficient, and the gas permeability of both phenyl and methyl silicones is low. A technology that can be used is desired.
  • Patent Document 3 and Patent Document 4 describe a method of suppressing silver corrosion by treating a light reflecting film made of silver or a silver alloy with a gas barrier surface treatment agent.
  • smectite a clay mineral
  • a water-soluble organic polymer such as carboxymethylcellulose salt
  • Patent Document 5 and Patent Document 6 describe a heat insulating glass unit containing a curable sealing material composition containing an inorganic-organic nanocomposite in which layered inorganic nanoparticles such as clay minerals are blended with polyorganosiloxane. However, it does not describe any optical materials.
  • JP 2010-1335 A Special table 2009-527622 JP 2012-251204 A JP 2012-251205 A JP 2009-523691 A JP 2009-523892 A
  • An object of the present invention is to solve the problems of conventional polyorganosiloxane, and to provide an optical material using a polyorganosiloxane composition having low gas permeability and good heat resistance.
  • the purpose of the present invention is to A curable polyorganosiloxane composition, and This is achieved by an optical material composed of a layered clay mineral treated with a compound having an ionic functional group.
  • the curable polyorganosiloxane composition is preferably hydrosilylation reaction curable or condensation reaction curable.
  • the layered clay minerals include montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, bedellite, vorconskite, laponite, hectorite, saponite, soconite, magadite, kenyaite, sobokite, subindulite, stevensite It is preferably selected from the group consisting of vermiculite, halloysite, aluminate oxide, hydrotalcite, illite, rectolite, tarosovite, ladykite, kaolinite, and mixtures thereof.
  • the ionic functional group is preferably a cationic group.
  • the cationic group is selected from the group consisting of ammonium, phosphonium, imidazolium, and pyridinium.
  • the compound having an ionic functional group has the following average structural formula (R M 3 SiO 1/2 ) a (R D 2 SiO 2/2 ) b (R T SiO 3/2 ) c (SiO 4/2 ) d ⁇
  • R M , R D, and R T are each independently a monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxy group, and —Z— (Q) n , wherein Z is a (n + 1) valent group.
  • 50 mol% or more is a monovalent hydrocarbon group, and at least one group represented by —Z— (Q) n is present in the molecule.
  • Including a, b, c and d are each independently 0 or a positive number, and a + b + c + d is a number in the range of 2 to 1000 ⁇ It is preferable that it is silicone represented by these.
  • Q is preferably a cationic group.
  • the Q is preferably selected from the group consisting of ammonium, phosphonium, imidazolium, and pyridinium.
  • the optical material of the present invention preferably further contains a phosphor.
  • the optical material of the present invention is preferably for an optical semiconductor.
  • the optical material of the present invention is preferably used as an optical semiconductor sealing agent, an optical semiconductor element protective agent, or a light reflecting film protective agent.
  • the present invention also relates to an optical article provided with the above optical material or a cured product thereof.
  • the present invention also relates to the use of a layered clay mineral treated with a compound having an ionic functional group for improving the gas barrier property of an optical material comprising a curable polyorganosiloxane composition.
  • the present invention is a method for improving gas barrier properties of an optical material comprising a curable polyorganosiloxane composition, wherein the curable polyorganosiloxane composition is treated with a compound having an ionic functional group. It also relates to the method of blending minerals.
  • the optical material of the present invention has low gas permeability and good heat resistance. Therefore, according to the present invention, an optical material having low gas permeability and good heat resistance can be provided.
  • the optical material of the present invention can be used, for example, as an optical semiconductor sealing agent, an optical semiconductor element protective film, or a light reflecting film protective agent.
  • the optical article of the present invention includes the optical material or a cured product thereof, has low gas permeability, and good heat resistance.
  • the present invention for example, discoloration or corrosion of silver or a silver alloy used in an electronic device, a lighting device including a light emitting diode, or the like can be sufficiently prevented.
  • a surface treating agent capable of giving excellent color fastness to a silver vapor deposition surface.
  • the present inventors have used a curable polyorganosiloxane composition and a layered clay mineral treated with a compound having an ionic functional group in combination, thereby improving the gas gallicity of an optical material including these. As a result, the present invention has been completed.
  • the optical material of the present invention contains a curable polyorganosiloxane composition.
  • the curing type of the polyorganosiloxane composition is not particularly limited, and examples thereof include known curing types such as peroxide curing type, hydrosilylation reaction (addition reaction) curing type, condensation reaction curing type, and ultraviolet curing type.
  • the curable polyorganosiloxane composition is preferably hydrosilylation reaction curable or condensation reaction curable.
  • the curable polyorganosiloxane composition is generally (A) a polyorganosiloxane containing at least two alkenyl groups in one molecule, and (B) in one molecule.
  • Component polyorganosiloxane is the main component of the curable polyorganosiloxane composition and has at least two silicon-bonded alkenyl groups in one molecule.
  • alkenyl group include a vinyl group, an allyl group, and a propenyl group.
  • Examples of the organic group other than the alkenyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, Alkyl groups exemplified by dodecyl group and the like; aryl groups exemplified by phenyl group and tolyl group; aralkyl groups such as benzyl group and ⁇ -phenylethyl group; 3,3,3-trifluoropropyl group, 3-chloro And halogen-substituted alkyl groups exemplified by propyl group.
  • the molecular structure of the component (A) may be linear, branched linear, cyclic, or network, and two or more polyorganosiloxanes may be used in combination.
  • the molecular weight of the component (A) is not particularly limited, and it can be used from a liquid having a low viscosity to a raw rubber having a high viscosity.
  • the (B) component polyorganosiloxane is a crosslinking agent for the curable polyorganosiloxane composition.
  • C) In the presence of a hydrosilylation reaction catalyst, the silicon-bonded hydrogen atom in the (B) component is replaced by the (A) component. It crosslinks and cures by addition reaction with the silicon-bonded alkenyl group.
  • the polyorganosiloxane (organohydrogenpolysiloxane) as the component (B) has at least two silicon-bonded hydrogen atoms in one molecule.
  • organic groups other than silicon-bonded hydrogen atoms include alkyl groups exemplified by methyl, ethyl, propyl, etc .; aryl groups exemplified by phenyl, tolyl, etc .; 3,3,3-trifluoropropyl Group, a substituted alkyl group exemplified by 3-chloropropyl group and the like.
  • the molecular structure of component (B) may be linear, branched linear, cyclic, or network, and two or more polyorganosiloxanes may be used in combination.
  • the molecular weight of component (B) is not particularly limited, but the viscosity at 25 ° C. is preferably in the range of 3 to 10,000 centipoise.
  • the blending amount of the component (B) is such that the ratio of the number of moles of silicon-bonded hydrogen atoms in the component (B) to the number of moles of silicon-bonded alkenyl groups in the component (A) is (0.5: 1).
  • the amount is such that ⁇ (20: 1), preferably (1: 1) to (3: 1). This is because if the number of moles of silicon-bonded hydrogen atoms in component (B) is less than 0.5 relative to the number of moles of silicon-bonded alkenyl groups in component (A), the composition can be cured sufficiently. This is because the cured product may foam if it is not greater than 20.
  • the hydrosilylation reaction catalyst is a catalyst for curing a hydrosilylation reaction (addition reaction) curable silicone composition.
  • a conventionally known catalyst can be used.
  • chloroplatinic acid an alcohol solution of chloroplatinic acid, a complex compound of chloroplatinic acid and olefins, vinyl siloxane or acetylene compound
  • platinum catalysts such as platinum black and platinum supported on a solid surface
  • palladium catalysts such as tetrakis (triphenylphosphine) palladium
  • rhodium catalysts such as chlorotris (triphenylphosphine) rhodium.
  • platinum-based catalysts are preferred.
  • Component (C) is preferably blended in an amount of 0.1 to 500 parts by mass in terms of catalytic metal element with respect to 1 million parts by mass of the total amount of components (A) and (B). This is because if the amount is less than 0.1 parts by mass, curing does not proceed sufficiently, and if it exceeds 500 parts by mass, it may be uneconomical.
  • the curable polyorganosiloxane composition may contain a curing retarder in order to adjust its curing rate or working life.
  • the retarder include carbon such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, phenylbutynol, and 1-ethynyl-1-cyclohexanol.
  • Alcohol derivatives having a carbon triple bond include enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahexenyl Low molecular weight siloxane containing alkenyl groups such as cyclotetrasiloxane; Alkynes such as methyl-tris (3-methyl-1-butyne-3-oxy) silane, vinyl-tris (3-methyl-1-butyne-3-oxy) silane Illustrative examples include silanes.
  • the blending amount of the curing retarder is appropriately selected according to the method of using the hydrosilylation reaction (addition reaction) curable composition, the molding method, and the like.
  • the general blending amount is in the range of 0.001% to 5% by mass based on the total mass of the hydrosilylation reaction (addition reaction) curable composition.
  • the curable polyorganosiloxane composition is, for example, (D) a diorganopolysiloxane having a molecular chain terminal blocked with a silanol group or a silicon atom-bonded hydrolyzable group, or a silicon atom bond A partially hydrolyzed condensate of an organosilane having a hydrolyzable group, an organosilane-based or organosiloxane-based crosslinking agent having a sufficient amount of silicon-bonded hydrolyzable groups to crosslink the components (E) and (D), And (F) a necessary amount of the condensation reaction accelerating catalyst.
  • the cured product can be obtained, for example, by curing the composition at room temperature or by heating.
  • the silicon-bonded hydrolyzable group in component (D) is sometimes referred to as a ketoximo group [ketoximino group such as dimethylketoximo group or methylethylketoximo group, and has a general formula: —O—N ⁇ CR′R A group represented by “(wherein R ′ and R” are the same or different alkyl groups, preferably an alkyl group having 1 to 6 carbon atoms); an alkoxy group such as a methoxy group or an ethoxy group; an acetoxy group An acyloxy group such as N-butylamino group, N, N-diethylamino group; an acylamide group such as N-methylacetamide group; an N, N-dialkylaminoxy group such as N, N-diethylaminoxy group An alkenyloxy group such as a propenoxy group is exemplified. Among these, an alkoxy group and a ketoximo group are preferable.
  • component (D) specifically, dimethylpolysiloxane, methylalkylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, methyl (both ends of the molecular chain blocked with silanol groups, silicon atom-bonded methoxy groups or ethoxy groups, methyl ( 3,3,3-trifluoropropyl) polysiloxane or partially hydrolyzed condensate of alkoxysilane, etc. are exemplified, but partial hydrolysis of dimethylpolysiloxane or alkoxysilane in terms of properties and economy of the cured product Condensates are preferred.
  • the terminal group of dimethylpolysiloxane blocked with a silicon atom-bonded methoxy group or ethoxy group includes methyldimethoxysiloxy group, methyldiethoxysiloxy group, trimethoxysiloxy group, triethoxysiloxy group, methyldimethoxysilylethyl (dimethyl).
  • the component (D) two or more kinds of partial hydrolysis condensates of diorganopolysiloxane or organosilane may be used in combination.
  • examples thereof include a mixture of dimethylpolysiloxanes in which both ends of a molecular chain are blocked with silanol groups.
  • the mixing ratio of the component (D-1) and the component (D-2) is preferably in the range of 1/99 to 10/90 by mass ratio.
  • Component (E) is a crosslinking agent for component (D) and has at least two, preferably three or four silicon atom-bonded hydrolyzable groups.
  • R y SiX 4-y (wherein R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, X is a silicon-bonded hydrolyzable group, and y is 0 or 1)) or an organosiloxane oligomer that is a partial hydrolysis condensate of the organosilane.
  • R is a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • X is a silicon-bonded hydrolyzable group
  • y is 0 or 1
  • organosiloxane oligomer that is a partial hydrolysis condensate of the organosilane.
  • the definition and illustration of a monovalent hydrocarbon group are as follows.
  • the silicon atom-bonded hydrolyzable group is a ketoximo group such as a dimethylketoximo group or a methylethylketoximo group [sometimes called a ketoximino group, a group represented by the general formula: —O—N ⁇ CR′R ′′.
  • R ′ and R ′′ are the same or different alkyl groups, preferably alkyl groups having 1 to 6 carbon atoms); alkoxy groups such as methoxy groups and ethoxy groups; acyloxy groups such as acetoxy groups; Alkylamino groups such as N-butylamino group and N, N-diethylamino group; acylamide groups such as N-methylacetamide group; N, N-dialkylaminoxy groups such as N, N-diethylaminoxy group; propenoxy groups and the like
  • An alkenyloxy group is exemplified. Among these, an alkoxy group and a ketoximo group are preferable.
  • component (E) examples include tetramethoxysilane, tetraethoxysilane, n-propyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltris (2 -Methoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, bis- [3- (triethoxysilyl) -propyl] tetrasulfide, bis- [3- (triethoxysilyl) -Propyl] disulfide, triethoxysilylpropyl-methacrylate-monosulfide, tetrakis (methylethylketoximo) silane, methyltris (methylethylketoximo) silane, vinyltri
  • the amount of component (E) is sufficient to cure component (D). If the composition is a one-component composition, it can be stored for a long period of time under moisture shielding and is exposed to moisture. The amount that can be cured at room temperature is usually in the range of 2 to 30% by mass. Specifically, the blending amount of the component (E) is, for example, 5 to 100 parts by weight per 100 parts by weight of the component (D), and is preferably in the range of 8 to 40 parts by weight from the viewpoint of curability.
  • a conventionally known condensation reaction promoting catalyst can be used as the component (F).
  • Specific examples include organotin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate; tetra (i-propyl) titanate, Organic titanate compounds such as tetra (n-butyl) titanate, dibutoxybis (acetylacetonate) titanium, isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, bis (dioctylpyrophosphate) oxyacetate titanate; tetrabutylzirconate , Tetrakis (acetylacetonato) zirconium, tet
  • component (F) is sufficient to promote the condensation reaction of component (D) and component (E), for example, 0.1 to 15% by mass, and 1 to 8% by mass. It is preferable.
  • additives can be added to the curable polyorganosiloxane composition of the present invention as long as the objects and effects of the present invention are not impaired.
  • additives include silicon oxide such as titanium oxide, aluminum oxide, silica or quartz glass, various inorganic or organic light diffusing materials such as talc, calcium carbonate, melamine resin, CTU guanamine resin and benzoguanamine resin; glass, alumino Heat dissipation materials such as metal oxides such as silicates, metal nitrides such as aluminum nitride and boron nitride; in addition, anti-aging agents, radical inhibitors, UV absorbers, adhesion improvers, flame retardants, surfactants, storage Stabilizer, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, antioxidant, thermal stabilizer, conductivity imparting agent, antistatic agent, radiation blocker, nucleating agent, phosphorus peroxide decomposition Agents, lubricants, pigments, metal deactivators,
  • the addition amount of these additives is not particularly limited, but is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, and more preferably 1 to 10% by weight based on the total mass of the composition.
  • Each additive may be used alone or in combination of two or more. When two or more types are added, the amount of each additive may be the same or different.
  • the optical material of the present invention includes a layered clay mineral treated with a compound having an ionic functional group.
  • the number of ionic functional groups in the compound having an ionic functional group may be one or more.
  • the compound having an ionic functional group for treating the layered clay mineral may be one or more.
  • Layered clay minerals that can be used in the present invention are natural or synthetic phyllosilicates, in particular montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, magnesium montmorillonite, Nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite ), Sobockite, svindordite, stevensite, talc, mica, kaolinite, vermiculite, halloysite, alumina Tookishido (aluminate oxides), or hydrotalcite (hydrotalcites), and a smectic clay, such as a mixture thereof (smectic clays).
  • montmorillonite sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, magnesium montmorillonite, Nontronite, beidellite, volkonskoite, laponite, hectorit
  • useful nanoclays include micaceous minerals such as illite, and rectorite, tarosovite, ledikite, and illite and the clay minerals described above.
  • Mixed layered illite / smectite minerals such as mixtures with one or more. Any swellable that fully adsorbs organic molecules and increases the interlayer space between adjacent phyllosilicate platelets to at least about 5 angstroms, or at least about 10 angstroms (when the phyllosilicate is measured in the dry state) Layered materials can be used.
  • the clay mineral either natural or synthetic can be used, but a synthetic product is more preferable from the viewpoint of coloring by impurities.
  • the layered clay minerals include montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, bedellite, vorconskite, laponite, hectorite, saponite, soconite, magadite, kenyaite, sobokite, subindulite, stevensite And at least one selected from the group consisting of vermiculite, halloysite, aluminate oxide, hydrotalcite, illite, rectolite, talosobite, readykite, kaolinite, and mixtures thereof.
  • These layered clay minerals may be untreated or treated with a known silylating agent.
  • a hydroxyl group exists at the terminal of the clay mineral, and the hydroxyl group and the added silylating agent react to make the terminal hydrophobic.
  • hydrophilicity / hydrophobicity can be controlled by the kind and introduction ratio of the silylating agent.
  • silylating agents are not particularly limited, but include methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and dodecyltrimethoxy.
  • Examples include silane, octadecyltrimethoxysilane, and other alkoxysilanes having a functional group.
  • a method for introducing a silylating agent into clay for example, it is produced by mixing raw clay and a silylating agent and mixing them using mechanical means.
  • silylating agents can be used in combination with the treatment with an ionic treating agent described later.
  • silylated layered clay mineral is available from Hojung etc. as silane-treated montmorillonite or silane-treated organic bentonite.
  • the layered clay mineral used in the present invention is treated with a compound having an ionic functional group to be a modified clay.
  • the modified clay of the present invention is a layered clay mineral having exchangeable ions, for example, Na + , Ca 2+ , Al 3+ , Fe 2+ , Fe 3+ and Mg 2+ , and at least one having at least one ionic functional group. It can be obtained by contacting with a seed compound (ionic treatment agent). Thereby, the said ion contained in a layered clay mineral is substituted by the ion derived from an ionic functional group.
  • the compound having an ionic functional group is preferably in the form of a salt.
  • the ionic treatment agent examples include non-silicone ionic treatment agents, silicone ionic treatment agents, and mixtures thereof.
  • the combination of a non-silicone ionic treatment agent and a silicone ionic treatment agent or a combination of one or two or more kinds of treatment agents having different molecular weights improves the compatibility and dispersibility for curable silicones. It is possible to reduce the amount of the chemical treatment agent used and to increase the degree of freedom in composition design.
  • Non-silicone ionic treatment agent The ionic functional group in the non-silicone ionic treatment agent is preferably a cationic group.
  • the cationic group is preferably selected from the group consisting of ammonium, phosphonium, imidazolium and pyridinium.
  • Examples of (quaternary) ammonium include trimethyloctyl ammonium, trimethyl decyl ammonium, trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexamethyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, Dimethyldialkylammonium such as trimethylalkylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldioctadecadienylammonium, for example, methylbenzylhexadecylammonium, dimethyl Benzyl such as octadecylbenzylammonium Dialkyldialkylam
  • Preparation of the layered silicate containing quaternary ammonium may be performed according to, for example, the description of JP-A-6-24732. Specifically, a quaternary ammonium salt is added to a layered silicate that has been dispersed in a large amount of water in advance, and the mixture is stirred, so that cations such as alkali metal ions and alkaline earth metal ions contained in the layered silicate can be obtained. Examples include a method of exchanging with quaternary ammonium.
  • Examples of the content of quaternary ammonium in the layered silicate containing quaternary ammonium include a ratio of 0.1 to 200% with respect to the cation exchange capacity of the layered silicate.
  • clay mineral treated with quaternary ammonium for example, a commercially available product such as Sven NZ70 (manufactured by Hojun Co., Ltd.) in which dimethyloctadecylbenzyl quaternary ammonium ion is introduced into natural montmorillonite can be used.
  • Sven NZ70 manufactured by Hojun Co., Ltd.
  • phosphonium examples include tributylhexadecylphosphonium, benzyltriphenylphosphonium, methyltriphenylphosphonium, bis (hydroxypropyl) octadecylisobutylphosphonium, triphenyl (tetradecyl) phosphonium, tetraphenylphosphonium, dodecyltris (4-phenoxyphenyl) Examples include phosphonium and octadecyltris (4-phenoxyphenyl) phosphonium.
  • imidazolium examples include 1-ethyl-3-methylimidazolium, 1-propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, Examples include hexadecyl-3-methylimidazolium.
  • the ionic functional group preferably contains one or more long-chain alkyl groups having 10 or more carbon atoms or an aromatic group in the molecule.
  • the long chain alkyl group having 10 or more carbon atoms include C 10 to C 30 alkyl groups.
  • the aromatic group include aryl groups exemplified by phenyl group, tolyl group and the like; aralkyl groups such as benzyl group and ⁇ -phenylethyl group; and arylene groups such as phenylene group.
  • the ionic functional group in the silicone-based ionic treatment agent is preferably a cationic group.
  • the cationic group is preferably selected from the group consisting of ammonium, phosphonium, imidazolium and pyridinium.
  • Ammonium-containing polyorganosiloxane can be used as the silicone-based ionic treatment agent.
  • ammonium-containing polyorganosiloxane examples include compounds described in US Pat. No. 5,130,396, which can be prepared from known substances including commercially available products. The contents of US Pat. No. 5,130,396 are incorporated herein by reference.
  • the ammonium-containing polyorganosiloxane of US Pat. No. 5,130,396 is represented by the following general formula (I): [Wherein R 1 and R 2 may be the same or different and represent a group of the following formula (II): ⁇ Wherein the nitrogen atom of formula (I) is bonded to the silicon atom of formula (II) via the R 5 group, R 5 represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, or a unit of the following general formula: (Wherein n is a number from 1 to 6 and represents the number of methylene groups at the nitrogen position, and m is a number from 0 to 6) And the free valence of the oxygen atom bonded to the silicon atom is as determined by the silicon atom of the other group of formula (II) and / or by the crosslinkable bond of one or more of the following formulas in the silica skeleton: Is saturated and (In the formula
  • R 4 is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a benzyl group, an alkyl group, a propargyl group, a chloroethyl group, a hydroxyethyl group, or A chloropropyl group
  • X is an anion having a valence x equal to 1 to 3, halide ion, hypochlorite ion, sulfate ion, hydrogen sulfate ion, nitrite ion, nitrate ion, phosphate ion, dihydrogen phosphate ion , Hydrogen phosphate ion, carbonate ion, bicarbonate ion, hydroxide ion, chlorate ion, perchlorate ion, chromate ion, dichromate ion, cyanide ion, cyanate ion,
  • One method of preparing ammonium-containing polyorganosiloxanes is to combine a primary, secondary, or tertiary aminosilane with water and at least one hydrolyzable alkoxy group, optionally in the presence of a catalyst, with water.
  • the reaction involves hydrolysis of the silane and subsequent condensation to produce an amine-terminated organopolysilane, which is then quaternized with a suitable quaternizing reagent such as mineral acid and / or alkyl halide to produce ammonium.
  • a suitable quaternizing reagent such as mineral acid and / or alkyl halide
  • a primary, secondary, or tertiary aminosilane having a hydrolyzable alkoxy group is quaternized prior to the hydrolytic condensation reaction to give a polyorganosiloxane.
  • the silane octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride available from Gelest, Inc.
  • subsequent hydrolysis / condensation gives the ammonium-containing polyorganosiloxane used herein.
  • tertiary aminosilanes useful for preparing ammonium-containing polyorganosiloxanes include tris (triethoxysilylpropyl) amine, tris (trimethoxysilylpropyl) amine, tris (diethoxymethylsilylpropyl). Examples include amines, tris (tripropoxysilylpropyl) amine, tris (ethoxydimethylsilylpropyl) amine, and tris (triethoxyphenylsilylpropyl) amine.
  • Useful amine-containing polyorganosiloxanes include compounds of the general formula: Wherein R 1 , R 2 , R 6 and R 7 are each independently H, a hydrocarbon group having 30 or less carbon atoms (for example, alkyl, cycloalkyl, aryl, aliphatic group-substituted aryl (alkaryl) R 1 and R 2 , or R 6 and R 7 together form a divalent bridging group having 12 or less carbon atoms, and R 3 and R 2.
  • n is 1 to 20, preferably 6-12.
  • amine-containing polyorganosiloxanes can be synthesized by known and conventional procedures, such as hydrosilylation, such as platinum-containing hydrosilylation catalysts, as described in US Pat. No. 5,026,890. It can be obtained by reacting an olefin amine such as allylamine with a polydiorganosiloxane having a Si—H bond in the presence of a catalyst, the contents of US Pat. No. 5,026,890 incorporated herein by reference. It is.
  • Specific amine-containing polyorganosiloxanes useful for preparing ammonium-containing polyorganosiloxanes include the following commercially available mixtures.
  • a phosphonium-containing polyorganosiloxane can be used as the silicone-based ionic treatment agent.
  • the phosphonium-containing polyorganosiloxane can be represented by the following general formula. (Wherein R 1 , R 2 , R 3 , R 4 , X, x are the same as above)
  • An imidazolium-containing polyorganosiloxane can be used as the silicone-based ionic treatment agent.
  • the imidazolium-containing polyorganosiloxane can be represented by the following general formula. (In the formula, R 1 , X and x are the same as above.)
  • Pyridinium-containing polyorganosiloxane can be used as the silicone-based ionic treatment agent.
  • the pyridinium-containing polyorganosiloxane can be represented by the following general formula. (In the formula, R 1 , R 2 , X and x are the same as above.)
  • the silicone-based ionic treatment agent is preferably the following average structural formula (R M 3 SiO 1/2 ) a (R D 2 SiO 2/2 ) b (R T SiO 3/2 ) c (SiO 4/2 ) d ⁇
  • R M , R D, and R T are each independently a monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxy group, and —Z— (Q) n , wherein Z is a (n + 1) valent group.
  • 50 mol% or more is a monovalent hydrocarbon group, and at least one group represented by —Z— (Q) n is present in the molecule.
  • Including a, b, c and d are each independently 0 or a positive number, and a + b + c + d is a number in the range of 2 to 1000 ⁇ Can be used.
  • the monovalent hydrocarbon group is linear, partially branched, branched, network or dendritic, substituted or unsubstituted, methyl group, ethyl group, propyl group, butyl group, pentyl Group, hexyl group and other alkyl groups; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and other alkenyl groups; phenyl group, tolyl group, xylyl group and other aryl groups; benzyl group, phenethyl group and the like And haloalkyl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group.
  • the number of carbon atoms of the monovalent hydrocarbon group is not particularly limited, but is preferably 1 to 30, more preferably 1 to 10, and still more preferably 1 to 6.
  • b is 2 to 1000, but it is preferably 2 to 500, more preferably 2 to 250, still more preferably 2 to 100, and 2 to 50. Even more preferably.
  • Q is preferably a cationic group.
  • Q is preferably selected from the group consisting of ammonium, phosphonium, imidazolium and pyridinium.
  • optical material of the present invention can be produced by mixing a curable polyorganosiloxane composition and a layered clay mineral treated with a compound having an ionic functional group.
  • the mixing ratio of the curable polyorganosiloxane and the layered clay mineral treated with the compound having an ionic functional group is not particularly limited, but curable polyorganosiloxane: treated with a compound having an ionic functional group
  • the mass (weight) ratio of the layered clay mineral is preferably in the range of 1:99 to 95: 5, in the range of 2.5: 97.5 to 90:10, in the range of 5:95 to 85:15.
  • a range of 5: 92.5 to 80:20, a range of 10:90 to 75:25, and a range of 12.5: 87.5 to 70:30 are more preferable.
  • the optical material of the present invention can contain at least one phosphor.
  • the phosphor is an inorganic fine particle, nanocrystal structure, quantum dot or the like that emits fluorescence having a wavelength longer than the wavelength of the excitation light when ultraviolet or visible excitation light is incident, and particularly has an excitation band at a wavelength of 300 to 500 nm.
  • Fluorescent light having a light emission peak at a wavelength of 380 to 780 nm, particularly blue (wavelength 440 to 480 nm), green (wavelength 500 to 540 nm), yellow (wavelength 540 to 595 nm), or red (wavelength 600 to 700 nm) It is preferable to use body fine particles.
  • phosphor fine particles As phosphor fine particles generally available on the market, garnets such as YAG and other oxides, nitrides, oxynitrides, sulfides, oxysulfides, rare earth sulfides, Y 3 Al 5 O 12 : Ce, ( Y, Gd) 3 Al 5 O 12 : Ce, Y 3 (Al, Ga) 5 O 12 : Rare earth aluminate chlorides and halophosphoric acid mainly activated by lanthanoid elements such as Ce represented by Ce The thing which consists of chlorides etc. is mentioned. Specific examples of these phosphor fine particles include inorganic phosphor fine particles disclosed in Japanese Patent Application Laid-Open No. 2012-052018.
  • the phosphor is generally in the form of fine particles having an average particle diameter in the range of 0.1 to 300 ⁇ m, and may be treated in a state of a mixture with glass powder such as glass beads. Furthermore, it may be used for processing a mixture of a plurality of phosphor fine particles in accordance with the wavelength range of excitation light or light emission. For example, when white light is obtained by irradiating ultraviolet excitation light, it is desirable to surface-treat a mixture of phosphor fine particles that emit blue, green, yellow, and red fluorescence.
  • An aspect of the present invention is the use of a layered clay mineral treated with a compound having an ionic functional group for improving the gas barrier property of an optical material comprising a curable polyorganosiloxane composition.
  • Still another aspect of the present invention is a method for improving gas barrier properties of an optical material comprising a curable polyorganosiloxane composition, wherein the curable polyorganosiloxane composition is treated with a compound having an ionic functional group. This is a method of blending the layered clay mineral.
  • the use and method of the present invention can improve the gas barrier properties of an optical material comprising a cured product of a curable polyorganosiloxane composition.
  • the optical material of the present invention can be used for any optical application, but is preferably used for an optical semiconductor.
  • the optical material of the present invention can be suitably used as a sealing agent for an optical semiconductor, a protective film for an optical semiconductor element, or a protective agent for a light reflecting film.
  • optical semiconductors or optical semiconductor elements include light emitting diode (LED) elements, semiconductor laser elements, organic EL, photodiode elements, phototransistor elements, solid-state imaging elements, light emitting elements for photocouplers, light receiving elements, and the like. Illustrated.
  • the optical material of the present invention can be suitably used for an optical semiconductor device.
  • the optical semiconductor element on the substrate or the optical semiconductor element in the housing is sealed or protected by the optical material of the present invention, or the light reflecting film is the main film. It is preferable that the surface is treated and protected by the optical material of the invention.
  • an optical article having excellent gas barrier properties and heat resistance can be produced.
  • curing type of the curable polyorganosiloxane composition in the optical material of the present invention curing can be performed, for example, at room temperature or under heating, based on a normal mode.
  • the optical article include a light emitting diode and an organic EL.
  • the curable polyorganosiloxane composition was heated at 150 ° C. for 2 hours to prepare a cured product having a thickness of 1 mm.
  • the water vapor permeability of the cured product was measured at 40 ° C. using a water vapor permeability measuring device manufactured by Illinois Instruments.
  • the water-vapor-permeation rate was measured about the hardened
  • the water vapor permeability in terms of 1 mm thickness of the cured product was determined by the following formula.
  • Example 1 As the modified clay, a commercially available product esben NZ70 (produced by Hojun Co., Ltd., dimethyloctadecylbenzyl quaternary ammonium ion exchange modified clay) in which dimethyloctadecylbenzyl quaternary ammonium ion was introduced into natural montmorillonite was used. 30.75 g of toluene was added to 1 g of the modified clay to make it uniform.
  • esben NZ70 produced by Hojun Co., Ltd., dimethyloctadecylbenzyl quaternary ammonium ion exchange modified clay
  • phenyl-based hydrosilylation reaction-curable silicone composition OE-6630 manufactured by Toray Dow Corning Co., Ltd., water vapor permeability 12.5 g / m 2 day
  • OE-6630 manufactured by Toray Dow Corning Co., Ltd., water vapor permeability 12.5 g / m 2 day
  • the water vapor permeability of the obtained cured product was 8.9 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the phenyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 100%, and the heat resistance was good.
  • Table 1 shows the measurement results of water vapor permeability and heat resistance.
  • Example 2 A cured product was obtained in the same manner as in Example 1, except that 2 g of Sven NZ70, 61.5 g of toluene, and 8 g of OE-6630 were changed.
  • the water vapor permeability of the obtained cured product was 7.6 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the phenyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 100%, and the heat resistance was good.
  • Table 1 shows the measurement results of water vapor permeability and heat resistance.
  • Example 3 A cured product was obtained in the same procedure as in Example 1 except that 3 g of Sven NZ70, 92.25 g of toluene and 7 g of OE-6630 were changed.
  • the water vapor permeability of the obtained cured product was 4.7 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the phenyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 100%, and the heat resistance was good.
  • Table 1 shows the measurement results of water vapor permeability and heat resistance.
  • Example 4 As the modified clay, a commercially available product Sven NZ70 (manufactured by Hojun Co., Ltd.) in which dimethyloctadecylbenzyl quaternary ammonium ion was introduced into natural montmorillonite was used. 61.5 g of toluene was added to 2 g of the modified clay to make it uniform. Thereafter, 11.4 g of a phenyl condensation reaction-curable silicone composition (water vapor permeability 16.3 g / m 2 day) represented by an average structural formula (PhSiO 3/2 ) 0.41 (PhMeSiO 2/2 ) 0.59 % Toluene solution was added to make uniform.
  • Sven NZ70 manufactured by Hojun Co., Ltd.
  • Example 5 ⁇ Creation of modified clay 1> 0.625 g of bentonite, Kunipia F (Kunimine Kogyo Co., Ltd., cation exchange capacity: 115 meq / 100 g) was dispersed in 25 g of water. Next, a solution prepared by dissolving 0.325 g of 1-hexadecyl 3-methylimidazolium chloride in 8 g of water was added dropwise little by little with stirring. 20 g of water was added, and the mixture was stirred for 3 hours to exchange the clay layer with 1-hexadecyl 3-methylimidazolium ion. Next, the solid-liquid was separated by centrifugation and washed 3 times with 20 g of water. The obtained product was sufficiently dried in an oven and then pulverized to obtain 1-hexadecyl 3-methylimidazolium ion exchange modified clay.
  • Example 7 ⁇ Creation of modified clay 3> Except for changing 0.48 g of tributylhexadecylphosphonium bromide used in ⁇ Creation of modified clay 2> of Example 6 to 0.51 g of triphenyl (tetradecyl) phosphonium bromide, Triphenyl (tetradecyl) phosphonium ion exchange modified clay was obtained.
  • ⁇ Creation of cured product 3> Except for changing the tributylhexadecylphosphonium ion exchange modified clay used in ⁇ Creation of cured product 2> in Example 6 to triphenyl (tetradecyl) phosphonium ion exchange clay obtained in ⁇ Creation of modified clay 3>, A cured product was obtained in the same procedure as in Example 6. The obtained cured product had a light transmittance retention of 96% after being heated at 150 ° C. for 24 hours, and had good heat resistance. Table 2 shows the measurement results of heat resistance.
  • Teflon trademark
  • the water vapor permeability of the obtained cured product was 62.1 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the methyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 98%, and the heat resistance was good. Table 3 shows the measurement results of water vapor permeability and heat resistance.
  • Example 9 A cured product was obtained in the same procedure as in Example 8, except that the amount of the ammonium-modified silicone exchange-modified clay (1) used in Example 8 was changed to 1 g and the amount of OE-6370M was changed to 4 g.
  • the water vapor permeability of the obtained cured product was 63.7 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the methyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 97%, and the heat resistance was good. Table 3 shows the measurement results of water vapor permeability and heat resistance.
  • Example 10 A cured product was obtained in the same procedure as in Example 8, except that the amount of the ammonium-modified silicone exchange-modified clay (1) used in Example 8 was changed to 1.5 g and the amount of OE-6370M was changed to 3.5 g. .
  • the water vapor permeability of the obtained cured product was 51.1 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the methyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 94%, and the heat resistance was good. Table 3 shows the measurement results of water vapor permeability and heat resistance.
  • Example 11 A mixture of platinum and 1,3-divinyltetramethyldisiloxane was added to a mixture of 8.49 g (55.5 mmol) of vinylbenzyl chloride and 30 g of toluene so that the amount of platinum metal was 2 ppm of solid content. Heat to 80 ° C., add 30 g (50.7 mmol) of one-end SiH functional heptadecamethyloctasiloxane represented by the general formula: Me 3 Si (OSiMe 2 ) 6 OSiMe 2 H, and drop at 105 ° C. for 1 hour. Stir with heating. Sampling and analysis by infrared absorption analysis revealed that the absorption of SiH groups disappeared and the reaction was complete.
  • the low boiling point substances were distilled off under reduced pressure by heating to obtain 35.2 g (yield 93.3%) of a cloudy light brown liquid.
  • the following formula is obtained by filtering twice with a 0.2 ⁇ m membrane filter. Was obtained as a light brown transparent liquid.
  • Teflon trademark
  • the water vapor permeability of the obtained cured product was 53.2 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the methyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 100%, and the heat resistance was good. Table 4 shows the measurement results of water vapor permeability and heat resistance.
  • Example 12 A cured product was obtained in the same procedure as in Example 11, except that 0.17 g of the ammonium-modified silicone exchange-modified clay (2) obtained in Example 11 and 0.1 g of OE-6370M were changed.
  • the water vapor permeability of the obtained cured product was 46.9 g / m 2 ⁇ day, and the gas barrier property was improved as compared with the methyl hydrosilylation reaction curable silicone composition to which no modified clay was added. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 89%, and the heat resistance was good.
  • Table 4 shows the measurement results of water vapor permeability and heat resistance.
  • Example 13 ⁇ Example of production of benzyltriphenylphosphonium-modified octasiloxane>
  • chloromethylphenyl-modified dimethyloctasiloxane was obtained.
  • 30 g (40.3 mmol) of the chloromethylphenyl-modified dimethyloctasiloxane, 10.6 g (40.3 mmol) of triphenylphosphine, 60 g of ethanol and 6 g of water were mixed and stirred while heating at 72 ° C. for 14.5 hours.
  • phosphonium modified silicone exchange modified clay > 0.7 g of bentonite, Kunipia F (Kunimine Kogyo Co., Ltd., cation exchange capacity: 115 meq / 100 g) was dispersed in 25 g of water. Next, an aqueous solution in which 0.97 g of the phosphonium-modified silicone obtained above was dispersed in 18.5 g of water was added dropwise little by little. 50 g of water was added, and the mixture was stirred for 3 hours to exchange the clay layer with phosphonium-modified silicone.
  • the obtained phosphonium-modified silicone exchange-modified clay can be added to the hydrosilylation reaction-curable silicone composition in the same manner as the ammonium silicone exchange-modified clay (2) in Example 11 or Example 12, and has gas barrier properties and heat resistance. Can be obtained.
  • Example 14 ⁇ Production of cured product 6> 2 g of toluene was added to 0.2 g of the phosphonium-modified silicone exchange-modified clay obtained above to make it uniform. Then average unit formula: ViMe 2 SiO (PhMeSiO) 20 SiMe 2 Vi 0.178 g of an organopolysiloxane represented by the formula: (HMe 2 SiO 1/2 ) 0.60 (PhSiO 3/2 ) 0.40 0.022 g of an organopolysiloxane represented by A curable composition containing 50% by weight of denatured clay by adding 1,3-divinyltetramethyldisiloxane complex of platinum in an amount of 100 ppm by weight of platinum metal based on the silicone content and mixing uniformly.
  • the curable composition was coated on a PET film and allowed to stand at room temperature for 24 hours to remove toluene, and then heated at 150 ° C. for 2 hours to obtain a cured product having a thickness of 40 ⁇ m.
  • the obtained cured product (thin film) had a water vapor permeability in terms of 1 mm thickness of 1.01 g / m 2 ⁇ day. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 100%, and the heat resistance was good.
  • Example 15 ⁇ Preparation of cured product 7> 3 g of toluene was added to 0.3 g of the phosphonium-modified silicone exchange-modified clay obtained above to make it uniform. Then average unit formula: ViMe 2 SiO (PhMeSiO) 20 SiMe 2 Vi 0.089 g of an organopolysiloxane represented by the formula: (HMe 2 SiO 1/2 ) 0.60 (PhSiO 3/2 ) 0.40 0.011 g of an organopolysiloxane represented by A composition containing 75% by weight of denatured clay was obtained by adding platinum 1,3-divinyltetramethyldisiloxane complex in an amount of 100 ppm by weight of platinum metal based on the silicone content and mixing uniformly.
  • the curable composition was coated on a PET film and allowed to stand at room temperature for 24 hours to remove toluene and then heated at 150 ° C. for 2 hours to obtain a cured product having a thickness of 50 ⁇ m.
  • the obtained cured product (thin film) had a water vapor permeability in terms of 1 mm thickness of 0.93 g / m 2 ⁇ day. Further, the light transmittance retention after heating at 150 ° C. for 24 hours was 80%, and the heat resistance was good.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte à un matériau optique qui contient une composition de polyorganosiloxane ayant une faible perméabilité aux gaz et une bonne résistance à la chaleur. Un matériau optique selon l'invention contient une composition de polyorganosiloxane durcissable, et un minéral argileux en couches traité à l'aide d'un composé ayant un groupe fonctionnel ionique.
PCT/JP2014/005888 2013-11-29 2014-11-25 Matériau optique Ceased WO2015079677A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015550562A JP6427107B2 (ja) 2013-11-29 2014-11-25 光学材料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2013247679 2013-11-29
JP2013-247679 2013-11-29
JP2014137335 2014-07-03
JP2014-137335 2014-07-03

Publications (1)

Publication Number Publication Date
WO2015079677A1 true WO2015079677A1 (fr) 2015-06-04

Family

ID=53198643

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/005888 Ceased WO2015079677A1 (fr) 2013-11-29 2014-11-25 Matériau optique

Country Status (3)

Country Link
JP (1) JP6427107B2 (fr)
TW (1) TWI647280B (fr)
WO (1) WO2015079677A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111670240A (zh) * 2018-01-30 2020-09-15 住友化学株式会社 组合物、膜、层叠体结构、发光装置和显示器
US20210189076A1 (en) * 2019-12-04 2021-06-24 Benq Materials Corporation Silicone film with gas barrier properties
JPWO2020080081A1 (ja) * 2018-10-18 2021-09-02 東亞合成株式会社 シルセスキオキサン誘導体組成物及びその利用
JP2022519094A (ja) * 2019-01-31 2022-03-18 エルケム・シリコーンズ・シャンハイ・カンパニー・リミテッド 優れた難燃性を備えた硬化性シリコーン組成物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108715685A (zh) * 2018-06-15 2018-10-30 广州市瑞合新材料科技有限公司 低透水率加成型液体硅橡胶及其制备方法
TWI849545B (zh) * 2022-10-24 2024-07-21 隆達電子股份有限公司 複合封裝材料及光學裝置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003286348A (ja) * 2002-03-28 2003-10-10 Toyota Central Res & Dev Lab Inc 樹脂複合材料の製造方法
JP2008045088A (ja) * 2006-08-21 2008-02-28 Sekisui Chem Co Ltd 光半導体用熱硬化性組成物、光半導体素子用封止剤、光半導体素子用ダイボンド材、光半導体素子用アンダーフィル材及び光半導体装置
JP2009137898A (ja) * 2007-12-07 2009-06-25 Lion Corp 毛髪化粧料
JP2013091705A (ja) * 2011-10-25 2013-05-16 Nitto Denko Corp シリコーン樹脂組成物、封止層、リフレクタおよび光半導体装置
JP2013159776A (ja) * 2012-02-09 2013-08-19 Adeka Corp ケイ素含有硬化性白色樹脂組成物及びその硬化物並びに該硬化物を用いた光半導体パッケージ及び反射材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003286348A (ja) * 2002-03-28 2003-10-10 Toyota Central Res & Dev Lab Inc 樹脂複合材料の製造方法
JP2008045088A (ja) * 2006-08-21 2008-02-28 Sekisui Chem Co Ltd 光半導体用熱硬化性組成物、光半導体素子用封止剤、光半導体素子用ダイボンド材、光半導体素子用アンダーフィル材及び光半導体装置
JP2009137898A (ja) * 2007-12-07 2009-06-25 Lion Corp 毛髪化粧料
JP2013091705A (ja) * 2011-10-25 2013-05-16 Nitto Denko Corp シリコーン樹脂組成物、封止層、リフレクタおよび光半導体装置
JP2013159776A (ja) * 2012-02-09 2013-08-19 Adeka Corp ケイ素含有硬化性白色樹脂組成物及びその硬化物並びに該硬化物を用いた光半導体パッケージ及び反射材料

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111670240A (zh) * 2018-01-30 2020-09-15 住友化学株式会社 组合物、膜、层叠体结构、发光装置和显示器
CN111670240B (zh) * 2018-01-30 2023-06-09 住友化学株式会社 组合物、膜、层叠体结构、发光装置和显示器
JPWO2020080081A1 (ja) * 2018-10-18 2021-09-02 東亞合成株式会社 シルセスキオキサン誘導体組成物及びその利用
JP7276348B2 (ja) 2018-10-18 2023-05-18 東亞合成株式会社 シルセスキオキサン誘導体組成物及びその利用
JP2022519094A (ja) * 2019-01-31 2022-03-18 エルケム・シリコーンズ・シャンハイ・カンパニー・リミテッド 優れた難燃性を備えた硬化性シリコーン組成物
JP7322157B2 (ja) 2019-01-31 2023-08-07 エルケム・シリコーンズ・シャンハイ・カンパニー・リミテッド 優れた難燃性を備えた硬化性シリコーン組成物
US20210189076A1 (en) * 2019-12-04 2021-06-24 Benq Materials Corporation Silicone film with gas barrier properties

Also Published As

Publication number Publication date
JP6427107B2 (ja) 2018-11-21
TWI647280B (zh) 2019-01-11
TW201525072A (zh) 2015-07-01
JPWO2015079677A1 (ja) 2017-03-16

Similar Documents

Publication Publication Date Title
JP6427107B2 (ja) 光学材料
JP6082267B2 (ja) 分岐状ポリシロキサンおよびこれらの使用
CA2637151C (fr) Composition scellante contenant un nanocomposite inorganique-organique
JP4636242B2 (ja) 光半導体素子封止材及び光半導体素子
CA2636163C (fr) Composition d'organopolysiloxane durcissable a temperature ambiante
JP6384841B2 (ja) Ｌｅｄ筐体用の硬化性シリコーンゴム組成物
JP6764376B2 (ja) シリコーン組成物及びその製造方法
EP1227133B1 (fr) Composition de caoutchouc de silicone durcissable à température ambiante
CN103298885B (zh) 透明性优异的导热性有机硅组合物及其固化物
EP3101062B1 (fr) Nanoparticule, procédé de production de nanoparticules, composition de résine de silicone à durcissement d'addition et appareil à semi-conducteur
JP5603237B2 (ja) 硬化性シリコーンラバー組成物および硬化したシリコーンラバー組成物ならびに官能性シリカを用いるそれらの調製方法
JP2010248413A (ja) 付加硬化型シリコーン樹脂組成物及び光半導体装置
KR20150037830A (ko) 경화성 오르가노폴리실록산 조성물, 그 제조 방법, 오르가노폴리실록산 경화물의 제조 방법, 오르가노폴리실록산의 축합 방법, 광 반도체 밀봉체, 및 오르가노폴리실록산의 축합 촉매
JP5500037B2 (ja) 難燃性オルガノポリシロキサン組成物
CN110741048B (zh) 硅酮组合物及其制备方法
Kopylov et al. Silica fillers for silicone rubber
JP6927655B2 (ja) 電気・電子部品保護用室温硬化性オルガノポリシロキサン組成物
WO2025062904A1 (fr) Composition de silicone et son procédé de production
JP6863878B2 (ja) 付加硬化型シリコーン組成物、硬化物、及び光学素子
TW202409206A (zh) 加成固化聚矽氧橡膠
TW202432715A (zh) 可混煉型矽酮橡膠組合物
WO2025142397A1 (fr) Composition de silicone durcissable aux ultraviolets pour stéréolithographie et produit durci associé
CN119421927A (zh) 可固化有机硅基凝胶组合物、其固化凝胶、包封剂、电子制品以及半导体芯片的保护方法

Legal Events

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

Ref document number: 14866751

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015550562

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14866751

Country of ref document: EP

Kind code of ref document: A1