JPWO2015079677A1 - Optical material - Google Patents

Abstract

Provided is an optical material using a polyorganosiloxane composition having low gas permeability and good heat resistance. An optical material comprising a curable polyorganosiloxane composition and a layered clay mineral treated with a compound having an ionic functional group.

Description

  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.

Usually, in 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. However, 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. There was a problem. Among 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. In addition, smectite, a clay mineral, is blended with a water-soluble organic polymer such as carboxymethylcellulose salt, and when used in a high-brightness LED having high light intensity and large heat generation, heat resistance is insufficient.

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 gazette 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 polyorganosiloxanes 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.

Preferably, 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

{Where
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 an (n + 1) valent group. A functional group or a direct bond to a silicon atom, n is a number of 1 or more, and Q is an ionic functional group), or a divalent functional group bonded to the Si atom of another siloxane unit However, of all R ^M , R ^D and R ^T , 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.

In the average structural formula, a to d are preferably a = 2, 2 <b <1000, c = 0, and d = 0, and at least one of R ^M is preferably —Z— (Q) _n .

  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.

  Furthermore, 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.

According to 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. In particular, according to the present invention, it is possible to provide a surface treating agent capable of giving excellent color fastness to a silver vapor deposition surface. According to the present invention, it is possible to provide a substrate made of silver or a silver alloy and having a light reflection film excellent in color fastness, and to improve light extraction efficiency and long-term stabilization of a light emitting device such as a light emitting diode. Can be achieved.

  As a result of intensive studies, 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.

[Curable polyorganosiloxane composition]
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. However, the curable polyorganosiloxane composition is preferably hydrosilylation reaction curable or condensation reaction curable.

In the case of hydrosilylation 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. A polyorganosiloxane having at least two silicon-bonded hydrogen atoms, (C) a hydrosilylation reaction catalyst.

  The (A) component polyorganosiloxane is a main component of the curable polyorganosiloxane composition, and has at least two silicon atom-bonded alkenyl groups in one molecule. Examples of the 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 β-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. Examples of 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-trifluorolopyr And a substituted alkyl group exemplified by a group, 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 the 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). It is the quantity which becomes-(20: 1), Preferably (1: 1)-(3: 1) is preferable. 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.

(C) The hydrosilylation reaction catalyst is a catalyst for curing a hydrosilylation reaction (addition reaction) curable silicone composition. As the hydrosilylation reaction catalyst of component (C), a conventionally known catalyst can be used. For example, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a complex compound of chloroplatinic acid and olefins, vinyl siloxane or acetylene compound Examples thereof include 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. Of these, platinum-based catalysts are preferred.

(C) The compounding quantity of a component has 0.1-500 mass parts in conversion of a catalyst metal element with respect to 1 million mass parts of total amounts of (A) component and (B) component. 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.

In the case of hydrosilylation reaction (addition reaction) curable, the curable polyorganosiloxane composition may contain a curing retarder in order to adjust its curing rate or working life. Examples of the curing retarder include carbon such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol, and the like. Alcohol derivatives having a carbon triple bond; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahexenyl Alkenyl such as methyl-tris (3-methyl-1-butyne-3-oxy) silane and 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.

In the case of condensation reaction curable, 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.

As the 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). ) Siloxy group, trimethoxysilylethyl (dimethyl) siloxy group and the like.

As the component (D), two or more kinds of partial hydrolysis condensates of diorganopolysiloxane or organosilane may be used in combination. For example, (D-1) dimethylpolysiloxane having both molecular chain ends blocked with silanol groups at 25 ° C. and a viscosity of 20 to 100 mPa · s and (D-2) viscosity at 25 ° C. of 1000 to 5000 mPa · s Examples thereof include a mixture of dimethylpolysiloxanes in which both ends of a molecular chain are blocked with silanol groups. Here, the mixing ratio of the component (D-1) and the component (D-2) is preferably in the range of 1/99 to 10/90 in terms of 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. General formula: R _y SiX _4-y (wherein R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, X is a silicon atom-bonded hydrolyzable group, and y is 0 or 1)) or an organosiloxane oligomer that is a partial hydrolysis condensate of the organosilane. In addition, 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 ″. (Wherein 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.

Examples of the component (E) 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, vinyltris (methylethylketo ) Silane, methyltriacetoxysilane, ethyltriacetoxysilane, methyl tri isopropenoxysilane silane, tetra isopropenoxysilane silane, methyltri (N, N-diethylamino) silane.

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. And an amount that can be cured at room temperature, and is usually in the range of 2 to 30% by mass. Specifically, the amount of component (E) is, for example, 5 to 100 parts by mass per 100 parts by mass of component (D), and a range of 8 to 40 parts by mass is preferable from the viewpoint of curability.

As the component (F), a conventionally known condensation reaction promoting catalyst can be used. Specific examples include organobutyl 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, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium Organic zirconium compounds such as zirconium naphthenate; Organoaluminum compounds such as tris (ethylacetoacetate) aluminum and tris (acetylacetonate) aluminum; Organic acid metal salts such as zinc naphthenate, cobalt naphthenate, and cobalt octylate; Examples thereof include amine catalysts such as ruamine and triethanolamine. An organotin compound or an organic titanate compound is suitable for a dealcoholization type condensation reaction curable composition, and an organic titanate compound is suitable for a deoxime type condensation reaction curable composition.

The blending amount of the component (F) is an amount sufficient to promote the condensation reaction of the component (D) and the component (E), for example, 0.1 to 15% by mass, and 1 to 8% by mass. It is preferable.

In addition, various 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. Examples of 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, physical property modifiers and the like.

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.

[Layered clay mineral treated with a compound having an ionic functional group]
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, Nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite ), Sobockite, svindordite, stevensite, talc, mica, kaolinite, vermiculite, halloysite, alumina Oxide (aluminate oxides), or hydrotalcite (hydrotalcites), and a smectic clay, such as a mixture thereof (smectic clays). In other embodiments, 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. As 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. In this case, the hydrophilicity / hydrophobicity can be controlled by the type and introduction ratio of the silylating agent.

Known 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. As 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. The treatment with these silylating agents can be used in combination with the treatment with an ionic treating agent described later. In addition, a well-known silylated layered clay mineral is available from Hojung etc. as silane-treated montmorillonite or silane-treated organic bentonite.

In order to improve the affinity with the curable polyorganosiloxane composition, 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.

Examples of the ionic treatment agent include non-silicone ionic treatment agents, silicone ionic treatment agents, and mixtures thereof. In particular, 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 Dialkyldialkylammonium such as realkylammonium and dibenzyldihexadecylammonium, trialkylmethylammonium such as trioctylmethylammonium, tridecylmethylammonium, tridecylmethylammonium, tritetradecylmethylammonium and trioctadecylmethylammonium Examples thereof include polyoxyethyl group-containing ammonium such as monohydroxy polyoxyethylene trialkyl ammonium, dihydroxy polyoxyethylene dialkyl ammonium, and trihydroxy polyoxyethylene alkyl ammonium.

  Preparation of the layered silicate containing quaternary ammonium may be performed according to the description of JP-A-6-24732, for example. 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.

  As content of the quaternary ammonium in the layered silicate containing a quaternary ammonium, the ratio of 0.1 to 200% can be mentioned with respect to the cation exchange capacity which a layered silicate has, for example.

As the 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.

Specific examples of phosphonium include tributylhexadecylphosphonium, benzyltriphenylphosphonium, methyltriphenylphosphonium, bis (hydroxypropyl) octadecylisobutylphosphonium, triphenyl (tetradecyl) phosphonium, tetraphenylphosphonium, dodecyltris (4-phenoxyphenyl) Examples include phosphonium and octadecyltris (4-phenoxyphenyl) phosphonium.

Specific examples of imidazolium 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.

From the viewpoint of compatibility with the curable polyorganosiloxane, 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. Examples of the long chain alkyl group having 10 or more carbon atoms include C _{10 to} C ₃₀ alkyl groups. Examples of the aromatic group include aryl groups exemplified by phenyl group, tolyl group and the like; aralkyl groups such as benzyl group and β-phenylethyl group; and arylene groups such as phenylene group.

(Silicone-based ionic treatment agent)
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.

  An ammonium-containing polyorganosiloxane can be used as the silicone-based ionic treatment agent.

  As an ammonium containing polyorganosiloxane, the compound described in the US Patent 5,130,396 is mentioned, for example, These can be prepared from the known substance containing a commercial item. The contents of US Pat. No. 5,130,396 are incorporated herein by reference.

〔式中、Ｒ^１及びＲ^２は、同一でも異なってもよく、以下の式（ＩＩ）の基を表わす：

｛ここで、式（I）の窒素原子はＲ^５基を介して式（II）のケイ素原子と結合し、
Ｒ^５は、炭素数１〜１０のアルキレン基、炭素数５〜８のシクロアルキレン基又は下記の一般式の単位を表わす：

（式中、ｎは、１〜６の数であり且つ窒素の位置におけるメチレン基の数を示し、ｍは、０〜６までの数である）
そして、ケイ素原子に結合した酸素原子の自由原子価は、式（II）の他の基のケイ素原子によって、及び／又は、一つ又は複数の下記式の架橋性結合によって、シリカ骨格における場合のように飽和されており、

（式中、Ｍは、ケイ素原子、チタン原子又はジルコニウム原子であり、
Ｒ’は、炭素数１〜５の直鎖状又は分岐状のアルキル基である）
そして、式(II）の基のケイ素原子対上記式の架橋性結合中の金属原子の比は、１：０〜１：１０である}
そして、式中、
Ｒ^３は、Ｒ^１又はＲ^２と同じであるか、或いは、水素、炭素数１〜２０の直鎖状若しくは分岐状のアルキル基、炭素数５〜８のシクロアルキル基、又は、ベンジル基であり、
Ｒ^４は、水素、炭素数１〜２０の直鎖状若しくは分岐状のアルキル基又は炭素数５〜８のシクロアルキル基、ベンジル基、アルキル基、プロパルギル基、クロロエチル基、ヒドロキシエチル基、又は、クロロプロピル基であり、
Ｘは、１から３に等しい価数ｘの陰イオンであり、ハロゲン化物イオン、次亜塩素酸イオン、硫酸イオン、硫酸水素イオン、亜硝酸イオン、硝酸イオン、リン酸イオン、リン酸二水素イオン、リン酸水素イオン、炭酸イオン、炭酸水素イオン、水酸化物イオン、塩素酸イオン、過塩素酸イオン、クロム酸イオン、二クロム酸イオン、シアン化物イオン、シアン酸イオン、ロダン化物イオン、硫化物イオン、硫化水素イオン、セレン化物イオン、テルル化物イオン、ホウ酸イオン、メタホウ酸イオン、アジ化物イオン、テトラフルオロホウ酸イオン、テトラフェニルホウ酸塩イオン、ヘキサフルオロリン酸イオン、ギ酸イオン、酢酸イオン、プロピオン酸イオン、シュウ酸イオン、トリフルオロ酢酸イオン、トリクロロ酢酸イオン又は安息香酸イオンの群から選択される。〕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:

(In the formula, n is a number from 1 to 6 and indicates 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, M is a silicon atom, a titanium atom or a zirconium atom,
R ′ is a linear or branched alkyl group having 1 to 5 carbon atoms)
And the ratio of the silicon atom of the group of formula (II) to the metal atom in the crosslinkable bond of the above formula is 1: 0 to 1:10}
And in the formula:
R ³ is the same as R ¹ or R ² , or is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a benzyl group. Yes,
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, rhodanide ion, sulfide Ion, hydrogen sulfide ion, selenide ion, telluride ion, borate ion, metaborate ion, azide ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, formate ion, acetate ion , Propionate ion, oxalate ion, trifluoroacetate ion, trichloroacetate ion or benzoic acid It is selected from the group of on. ]

  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 polyorganosiloxane containing product is obtained. This type of method is described in the aforementioned US Pat. No. 5,130,396. In this regard, US Pat. No. 6,730,766 describes a process for the production of quaternized polysiloxanes by reaction of epoxy functional polysiloxanes, the contents of US Pat. No. 6,730,766. Is incorporated herein by reference.

In this process variant, a primary, secondary, or tertiary aminosilane having a hydrolyzable alkoxy group is quaternized prior to the hydrolytic condensation reaction to give a polyorganosiloxane. . For example, ammonium-containing N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium chloride, and commercial ammonium-containing trialkoxy The silane octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (available from Gelest, Inc) and subsequent hydrolysis / condensation gives the ammonium-containing polyorganosiloxane used herein.

Other suitable 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.

（式中、Ｒ^１、Ｒ^２、Ｒ^６及びＲ^７は、個々独立して、Ｈ、炭素数３０以下の炭化水素基（例えば、アルキル、シクロアルキル、アリール、脂肪族基置換アリール（alkaryl）、芳香族基置換アルキル（aralkyl）など）であり、又はＲ^１とＲ^２は共に、又はＲ^６とＲ^７は共に、炭素数１２以下の二価の架橋基を形成し、Ｒ^３及びＲ^５は、個々独立して炭素数３０以下の二価の炭化水素架橋基であり、任意に１つ以上の酸素原子及び／又はチッ素原子を鎖の中に含有することができ、例えば、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｃ（ＣＨ_３）−ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−などのような炭素数１〜８の直鎖状又は分岐状のアルキレンであり、Ｒ^４は、個々独立してアルキル基であり、そしてｎは１〜２０であり、好ましくは６〜１２である。）Yet another method of preparing ammonium-containing polyorganosiloxanes requires quaternization of primary, secondary, or tertiary amine-containing polyorganosiloxanes with a quaternizing reagent. Is done. 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. ⁵ are each independently a divalent hydrocarbon bridging group having 30 or less carbon atoms, and can optionally contain one or more oxygen atoms and / or nitrogen atoms in the chain. _{CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, - CH 2 C (CH 3) -CH 2 -, - CH 2 CH 2 CH 2 CH 2 - carbon atoms, such as 1 8 is a linear or branched alkylene, R ⁴ is alkyl and each independently , And the and n is 1-20, preferably 6-12.)

  These and similar 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.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｘ、ｘは、上記と同じである。）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)

（式中、Ｒ^１、Ｘ、ｘは、上記と同じである。）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.)

（式中、Ｒ^１、Ｒ^２、Ｘ、ｘは、上記と同じである。）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

{Where
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 an (n + 1) valent group. A functional group or a direct bond to a silicon atom, n is a number of 1 or more, and Q is an ionic functional group), or a divalent functional group bonded to the Si atom of another siloxane unit However, of all R ^M , R ^D and R ^T , 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. Although carbon number of a monovalent hydrocarbon group is not specifically limited, 1-30 are preferable, 1-10 are more preferable, and 1-6 are still more preferable.

In the average structural formula, a to d are a = 2, 2 <b <1000, c = 0 and d = 0, and at least one of R ^M is preferably —Z— (Q) _n . In this case, it is sufficient that 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.

The following are illustrated as a silicone type ionic processing agent of such a structure.

[Optical materials]
The 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. In particular, the phosphor has an excitation band at a wavelength of 300 to 500 nm. Fluorescence which has a light emission peak at a wavelength of 380 to 780 nm, particularly blue (wavelength of 440 to 480 nm), green (wavelength of 500 to 540 nm), yellow (wavelength of 540 to 595 nm), or red (wavelength of 600 to 700 nm) It is preferable to use body 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 JP2012-052018A.

The phosphor is generally in the form of fine particles having an average particle diameter in the range of 0.1 to 300 μm, 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. In particular, 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.

Specific examples of 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.

In particular, the optical material of the present invention can be suitably used for an optical semiconductor device. In the optical semiconductor device using the optical material of the present invention, 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.

Further, by curing the optical material of the present invention, an optical article having excellent gas barrier properties and heat resistance can be produced. According to the 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. As an optical article, a light emitting diode, organic EL, etc. are mentioned, for example.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by these Examples. In the chemical formulas in the examples, “Me” is a methyl group, “Ph” is a phenyl group, and “Vi” is a vinyl group.

（上式中、ｎ層からなる多層コート（厚みL）において、第ｎ層の厚みと水蒸気透過率をそれぞれ、ｌ_１．P_ｎとしたときにフィルム全体の水蒸気透過率P_totalは、上記式より算出することができる。参考文献：高分子と水分 第7章 高分子学会編 幸書房（１９７３））[Water vapor permeability]
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.
Moreover, about the hardened | cured material of the thin film in Examples 14 and 15, the water-vapor-permeation rate was measured about the hardened | cured material of the thin film hardened | cured on the PET film. The water vapor permeability in terms of 1 mm thickness of the cured product was determined by the following formula.

(In the above formula, in the multilayer coat consisting of n layers (thickness L), when the thickness of the nth layer and the water vapor transmission rate are respectively l ₁ .P _n , the water vapor transmission rate P _total of the entire film is the above formula. References: Polymers and moisture Chapter 7: The Society of Polymer Science, Koshobo (1973))

[Heat-resistant]
The curable polyorganosiloxane composition was heated at 150 ° C. for 2 hours to produce a cured product having an optical path length of 0.2 mm. The light transmittance of the cured product at a wavelength of 600 nm was measured. Furthermore, this hardened | cured material was heated at 150 degreeC for 24 hours, and the light transmittance in wavelength 600nm was measured again. The heat resistance was evaluated from the light transmittance retention by the following formula.

Heat resistance (retention rate of light transmittance) =
(Transmittance after 24 hours at 150 ° C./Transmittance immediately after) x 100

[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. Thereafter, 9 g of a phenyl hydrosilylation reaction-curable silicone composition OE-6630 (manufactured by Toray Dow Corning Co., Ltd., water vapor permeability of 12.5 g / m ² day) was added and made uniform. It moved to the cup made from Teflon (trademark), and after removing toluene by leaving still at room temperature for 24 hours, it heated at 150 degreeC for 2 hours, and obtained hardened | cured material. 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 procedure 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. It moved to the cup made from Teflon (trademark), and after removing toluene by leaving still at room temperature for 24 hours, it heated at 170 degreeC for 2 hours, and obtained hardened | cured material. The water vapor permeability of the obtained cured product was 3.4 g / m ² · day, and the gas barrier property was improved as compared with the phenyl condensation 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. The measurement results of water vapor permeability and heat resistance are shown in Table 2.

[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 obtained 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 pulverized to obtain 1-hexadecyl 3-methylimidazolium ion-exchanged modified clay.

<Creation of cured product 1>
0.1 g of 1-hexadecyl 3-methylimidazolium ion exchange modified clay obtained above was dispersed in 1.9 g of toluene. Thereafter, 0.57 g of 70 wt% toluene of a 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 The solution was added and made uniform. It moved to the cup made from Teflon (trademark), and after removing toluene by leaving still at room temperature for 24 hours, it heated at 170 degreeC for 2 hours, and obtained hardened | cured material. The obtained cured product had a light transmittance retention of 100% after being heated at 150 ° C. for 24 hours, and had good heat resistance. Table 2 shows the measurement results of heat resistance.

[Example 6]
<Creation of modified clay 2>
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 obtained by dissolving 0.48 g of tributylhexadecylphosphonium bromide in 8 g of water was added dropwise little by little while stirring. 20 g of water was added, and the mixture was stirred for 3 hours to exchange the clay layer with tributylhexadecylphosphonium ions. 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 pulverized to obtain tributylhexadecylphosphonium ion exchange modified clay.

<Creation of cured product 2>
0.1 g of the tributylhexadecylphosphonium ion exchange modified clay obtained above was dispersed in 1.9 g of toluene. Thereafter, 0.57 g of 70 wt% toluene of a 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 The solution was added and made uniform. It moved to the cup made from Teflon (trademark), and after removing toluene by leaving still at room temperature for 24 hours, it heated at 170 degreeC for 2 hours, and obtained hardened | cured material. The obtained cured product had a light transmittance retention of 98% after being heated at 150 ° C. for 24 hours, and had good heat resistance. Table 2 shows the measurement results of heat resistance.

[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.

で表される片末端アミノシリコーンを１５ｇのイソプロピルアルコールに分散させた。[Example 8]
<Synthesis of ammonium-modified silicone 1>
9g following formula

Was dispersed in 15 g of isopropyl alcohol.

で示されるアンモニウム変性シリコーン溶液を得た。An aqueous solution prepared by dissolving 0.31 g of 35% hydrochloric acid in 10 g of water was added dropwise to the obtained dispersion, and the mixture was stirred for 30 minutes to obtain the following formula.

An ammonium-modified silicone solution represented by

<Creation of modified clay 4>
2.1 g of bentonite, Kunipia F (manufactured by Kunimine Kogyo Co., Ltd., cation exchange capacity: 115 meq / 100 g) was dispersed in 60 g of water. Next, 34.3 g of the ammonium-modified silicone solution obtained above was added dropwise little by little with stirring. 20 g of water was added and the mixture was stirred for 3 hours, and the clay layer was replaced with the ammonium-modified silicone. Next, the solid and liquid were separated by centrifugation, washed 3 times with 20 g of isopropyl alcohol, and further washed 3 times with water. The obtained product was sufficiently dried in an oven and pulverized to obtain an ammonium-modified silicone exchange-modified clay (1).

<Creation of cured product 4>
0.5 g of the ammonium-modified silicone exchange-modified clay (1) obtained above was dispersed in 5 g of toluene. Thereafter, OE-6370M (manufactured by Toray Dow Corning Co., Ltd., water vapor transmission rate 69.8 g / m ² day), which is a methyl hydrosilylation reaction-curable silicone composition, was added and made uniform. It moved to the cup made from Teflon (trademark), and after removing toluene by leaving still at room temperature for 24 hours, it heated at 150 degreeC for 2 hours, and obtained hardened | cured material. 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.

で表されるクロロメチルフェニル変性ジメチルオクタシロキサンを淡褐色の透明液体として得た。[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 μm membrane filter.

Was obtained as a light brown transparent liquid.

で表されるベンジルトリメチルアンモニウム塩変性ヘプタデカメチルオクタシロキサンを粘稠な液体として得た。10 grams (13.43 mmol) of the above chloromethylphenyl-modified dimethyloctasiloxane, 2.91 grams of trimethylamine aqueous solution (trimethylamine: 0.87 grams (14.8 mmol)) and 10 grams of ethanol were mixed and stirred with heating at 65-70 ° C. for 2 hours. Gram and 3.2 g of trimethylamine aqueous solution (trimethylamine: 0.96 g (16.2 mmol) were added and stirred for 4.5 hours. Low boiling point substances were distilled off under reduced pressure by heating, and 9.34 g (yield: 86,6%) of the following formula

A benzyltrimethylammonium salt-modified heptadecamethyloctasiloxane represented by the following formula was obtained as a viscous liquid.

<Making modified clay 5>
4.87 g of bentonite, Kunipia F (manufactured by Kunimine Kogyo Co., Ltd., cation exchange capacity: 115 meq / 100 g) was dispersed in 200 g of water. Next, an aqueous solution in which 5 g of the benzyltrimethylammonium salt-modified heptadecamethyloctasiloxane obtained above was dispersed in 15 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 benzyltrimethylammonium salt-modified heptadecamethyloctasiloxane. Next, the solid and liquid were separated by centrifugation, washed 3 times with 20 g of isopropyl alcohol, and further washed 3 times with water. The obtained product was sufficiently dried in an oven and pulverized to obtain an ammonium-modified silicone exchange-modified clay (2).

<Creation of cured product 5>
0.083 g of the ammonium modified silicone exchange modified clay (2) obtained above was dispersed in 1.7 g of toluene. Then, OE-6370M (manufactured by Toray Dow Corning Co., Ltd., water vapor permeability 69.8 g / m ² day), which is a methyl-based hydrosilylation reaction-curable silicone composition, was added to make uniform. It moved to the cup made from Teflon (trademark), and after removing toluene by leaving still at room temperature for 24 hours, it heated at 150 degreeC for 2 hours, and obtained hardened | cured material. 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.

[Comparative Example 1]
It was 12.5 g / m < ² > day as a result of measuring the water-vapor permeability of OE-6630 (made by Toray Dow Corning Co., Ltd.) which is a phenyl-type hydrosilylation reaction curable silicone composition. Table 1 shows the measurement results of water vapor permeability.

[Comparative Example 2]
The water vapor permeability of the phenyl condensation reaction curable silicone composition represented by the average structural formula (PhSiO _3/2 ) _0.41 (PhMeSiO _2/2 ) _0.59 was measured and found to be 16.3 g / m ² day. The measurement results of water vapor permeability are shown in Table 2.

[Comparative Example 3]
It was 69.8 g / m < ² > day as a result of measuring the water-vapor permeability of OE-6370M (made by Toray Dow Corning Co., Ltd.) which is a methyl-type hydrosilylation reaction curable silicone composition. Table 3 shows the measurement results of water vapor permeability.

[Comparative Example 4]
Carboball Ultrez 10 (manufactured by Nikko Chemicals), which is carboxymethyl cellulose, was dispersed in 20 g of water. It moved to the cup made from Teflon (trademark), and water was removed by leaving still at room temperature for 3 days. When heated at 150 ° C. for 24 hours and evaluated for heat resistance, it was clearly found that coloring occurred. The measurement results of heat resistance are shown in Tables 1-3.

[Comparative Example 5]
A clay mineral saponite, Smecton SA (manufactured by Kunimine Kogyo Co., Ltd.) 0.3 g, and carboxymethyl cellulose, carboball Ultrez 10 (manufactured by Nikko Chemicals) 0.2 g, are uniformly dispersed in 20 g of water and made of Teflon (registered trademark). It was transferred to a cup and left to stand at 50 ° C. for 3 days to remove water. When heated at 150 ° C. for 24 hours and evaluated for heat resistance, it was clearly found that coloring occurred. The measurement results of heat resistance are shown in Tables 1-3.

In addition, unless otherwise indicated, the compounding quantity of each component in Tables 1-3 represents a "mass part" ("weight part").

（１）ＯＥ−６６３０（東レ・ダウコーニング株式会社製）
（４）カーボボール Ultrez10（日光ケミカルズ製）
（５）エスベンＮＺ７０（株式会社ホージュン製）
（６）スメクトンＳＡ（クニミネ工業株式会社製）

(1) OE-6630 (Toray Dow Corning Co., Ltd.)
(4) Carboball Ultrez10 (Nikko Chemicals)
(5) Sven NZ70 (manufactured by Hojun Co., Ltd.)
(6) Smecton SA (Kunimine Industry Co., Ltd.)

（２）(PhSiO_3/2)_0.41(PhMeSiO_2/2)_0.59
（４）カーボボール Ultrez10（日光ケミカルズ製）
（５）エスベンＮＺ７０（株式会社ホージュン製）
（６）スメクトンＳＡ（クニミネ工業株式会社製）
From the results of Examples 1 to 3 and Comparative Example 1, it can be seen that the optical material of the present invention has a lower water vapor permeability. Moreover, from the results of Examples 1 to 3 and Comparative Examples 4 and 5, it can be seen that the optical material of the present invention has excellent heat resistance.

(2) (PhSiO _3/2 ) _0.41 (PhMeSiO _2/2 ) _0.59
(4) Carboball Ultrez10 (Nikko Chemicals)
(5) Sven NZ70 (manufactured by Hojun Co., Ltd.)
(6) Smecton SA (Kunimine Industry Co., Ltd.)

（３）ＯＥ−６３７０Ｍ（東レ・ダウコーニング株式会社製）
（４）カーボボール Ultrez10（日光ケミカルズ製）
（６）スメクトンＳＡ（クニミネ工業株式会社製）
From the results of Examples 4 to 7 and Comparative Example 2, it can be seen that the optical material of the present invention has a lower water vapor permeability. Moreover, from the results of Examples 4 to 7 and Comparative Examples 4 and 5, it can be seen that the optical material according to the present invention has excellent heat resistance.

(3) OE-6370M (Toray Dow Corning Co., Ltd.)
(4) Carboball Ultrez10 (Nikko Chemicals)
(6) Smecton SA (Kunimine Industry Co., Ltd.)

From the results of Examples 8 to 12 and Comparative Example 3, it can be seen that the optical material of the present invention has a lower water vapor permeability. Moreover, from the results of Examples 8 to 12 and Comparative Examples 4 and 5, it can be seen that the optical material of the present invention has excellent heat resistance.

で表されるベンジルトリフェニルホスホニウム塩変性ヘプタデカメチルオクタシロキサン（以下、ホスホニウム変性シリコーン）を固体状ペーストとして得た。[Example 13]
<Example of production of benzyltriphenylphosphonium-modified octasiloxane>
In the same manner as in Example 11, 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. Low-boiling substances are distilled off under reduced pressure by heating, and the following formula of 33.8 grams (yield: 83.3%)

A benzyltriphenylphosphonium salt-modified heptadecamethyloctasiloxane (hereinafter referred to as phosphonium-modified silicone) represented by the following formula was obtained as a solid paste.

<Creation of modified clay: 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. Next, the solid and liquid were separated by centrifugation, washed 3 times with 20 g of isopropyl alcohol, and further washed 3 times with water. The obtained product was sufficiently dried in an oven and then pulverized to obtain a phosphonium-modified silicone exchange-modified clay.

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 such an amount that platinum metal is 100 ppm by weight with respect to the silicone content and mixing uniformly. I got a thing.
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 μm.
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 1,3-divinyltetramethyldisiloxane complex of platinum in such an amount that platinum metal was 100 ppm by weight with respect to the silicone content, and mixing uniformly. Obtained.
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 μm.
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.

Claims (15)

A curable polyorganosiloxane composition, and
An optical material comprising a layered clay mineral treated with a compound having an ionic functional group. The optical material according to claim 1, wherein the curable polyorganosiloxane composition is hydrosilylation reaction curable or condensation reaction curable. The layered clay mineral is montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, bedellite, vorconskite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobokite, subindordite, stevensite The optical material according to claim 1, wherein the optical material is selected from the group consisting of: vermiculite, halloysite, aluminate oxide, hydrotalcite, illite, rectolite, talosobite, ladykite, kaolinite, and mixtures thereof. The optical material according to claim 1, wherein the ionic functional group is a cationic group. The optical material according to claim 4, wherein the cationic group is selected from the group consisting of ammonium, phosphonium, imidazolium, and pyridinium. The compound having the 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

{Where
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 an (n + 1) valent group. A functional group or a direct bond to a silicon atom, n is a number of 1 or more, and Q is an ionic functional group), or a divalent functional group bonded to the Si atom of another siloxane unit However, 50 mol% or more of all R ^M , R ^D and R ^T are monovalent hydrocarbon groups, 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. }
The optical material according to claim 1, which is a silicone represented by the formula: The optical material according to claim 6, wherein Q is a cationic group. The optical material according to claim 6 or 7, wherein Q is selected from the group consisting of ammonium, phosphonium, imidazolium, and pyridinium. In the average structural formula, a to d are a = 2, 2 <b <1000, c = 0 and d = 0, and at least one of R ^M is —Z— (Q) _n. The optical material in any one of -8. The optical material according to claim 1, further comprising a phosphor. The optical material according to claim 1, which is used for an optical semiconductor. The optical material according to any one of claims 1 to 11, which is an optical semiconductor sealing agent, an optical semiconductor element protective agent, or a light reflecting film protective agent. An optical article comprising the optical material according to claim 1 or a cured product thereof. Use of a layered clay mineral treated with a compound having an ionic functional group for improving gas barrier properties of an optical material comprising a curable polyorganosiloxane composition. A method for improving gas barrier properties of an optical material comprising a curable polyorganosiloxane composition, wherein a lamellar clay mineral treated with a compound having an ionic functional group is added to the curable polyorganosiloxane composition.