JP6497289B2 - Curable composition, cured product, and optical semiconductor device - Google Patents

Description

  The present invention relates to a curable composition, a cured product, and an optical semiconductor device.

  Silicone resins are widely used as sealing materials for semiconductor devices such as LEDs. The LED has a problem that the shape of the sealing material changes due to a thermal shock or a high temperature and high humidity environment that occurs during energization or lighting, and the life of the LED is reduced.

  As a technique for preventing a decrease in the lifetime of an LED due to such thermal shock, Patent Document 1 discloses an addition-type curable polysiloxane composition containing an alkenyl group-containing polysiloxane, a hydrogen polysiloxane, and an alkenyl complex of platinum. The platinum alkenyl complex is a platinum alkenyl complex obtained by reacting chloroplatinic acid hexahydrate with 6 equivalents or more of a bifunctional or higher alkenyl compound. Addition-type curable polysiloxane compositions in which the ratio of the number of alkenyl groups to the number of silicon-bonded hydrogen atoms in the hydrogen polysiloxane is 1.0 or more and 2.5 or less are disclosed.

WO2011 / 162294

  An object of the present invention is to provide a cured product whose shape hardly changes even under severe environments such as thermal shock and high temperature and high humidity, a curable composition capable of forming the cured product, and an optical semiconductor device having the cured product. And

The present invention includes, for example, the following [1] to [7].
[1] At least one inorganic oxide particle (A) selected from cerium oxide particles and iron (II) oxide particles, having at least two alkenyl groups per molecule, and having a silicon-bonded aryl group A polysiloxane (B), a polysiloxane (C) having at least two silicon-bonded hydrogen atoms per molecule, and a hydrosilylation catalyst (D),
Content of the said inorganic oxide particle (A) is less than 5 mass parts with respect to a total of 100 mass parts of the said polysiloxane (B) and the said polysiloxane (C), The curable composition characterized by the above-mentioned. .

[2] The content ratio of the aryl group contained in the polysiloxane (B) is 20 mol% or more with respect to 100 mol% of the total number of silicon atoms contained in the polysiloxane (B). [1] The curable composition according to [1].

[3] The curable composition according to any one of [1] or [2], wherein the polysiloxane (B) is a polysiloxane represented by the following formula (1).

(In Formula (1), R ¹ may be the same as or different from each other, and is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. 7 to 30 aralkyl groups, or groups in which the hydrogen atoms of these groups are replaced with hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, oxysilanyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 30 carbon atoms . plurality of at least two of R ¹ represents an alkenyl group having 2 to 10 carbon atoms, a plurality of at least one .X hydrogen atoms an aryl group of R ^1, or alkyl of 1 to 3 carbon atoms A and c each independently represents an integer of 1 or more, b, d and f each independently represents an integer of 0 or more, and c / (a + b + c + d) ≧ 0.2.

[4] The curable composition according to any one of [1] to [3], wherein the polysiloxane (C) has a structural unit represented by the following formula (2).

(In the formula (2), Ar represents an aryl group having 6 to 30 carbon atoms.)

[5] The curable composition according to any one of [1] to [4], further containing phosphor particles (E).

[6] A cured product obtained by curing the curable composition according to any one of [1] to [5].

[7] An optical semiconductor device having the cured product according to [6].

  The shape of the cured product of the present invention hardly changes even under severe environments such as thermal shock and high temperature and high humidity. According to the present invention, it is possible to provide a curable composition having the above characteristics, a cured product formed from the composition, and an optical semiconductor device having the cured product.

FIG. 1 is a schematic diagram showing a specific example of an optical semiconductor device. FIG. 2 is a schematic diagram showing a specific example of the optical semiconductor device.

Hereinafter, modes for carrying out the invention will be described including preferred embodiments.
1. Curable composition The curable composition of the present invention has at least two alkenyl groups per molecule of at least one inorganic oxide particle (A) selected from cerium oxide particles and iron (II) oxide particles. And a polysiloxane (B) having a silicon-bonded aryl group, a polysiloxane (C) having at least two silicon-bonded hydrogen atoms per molecule, and a hydrosilylation reaction catalyst (D),
Content of the said inorganic oxide particle (A) is 5 mass parts or less with respect to 100 mass parts of total amounts of the said polysiloxane (B) and the said polysiloxane (C), It is characterized by the above-mentioned.
Moreover, a fluorescent substance particle (E) and other components can be contained as needed.

1-1. Inorganic oxide particles (A)
The inorganic oxide particles (A) are at least one selected from cerium oxide particles and iron (II) oxide particles. Among these, cerium oxide particles are preferable.
The cerium oxide particles can be produced by a known method described in JP-A-4-300644. Specifically, a method of firing a cerium oxide precursor such as cerium carbonate or obtaining cerium oxide particles using an oxidizing agent; an aqueous solution of a cerium salt compound such as cerium nitrate or cerium ammonium nitrate with an alkali metal sodium salt or ammonia A method of obtaining cerium oxide particles by a sol-gel method to obtain a cerium oxide colloidal gel by reaction; a cerium oxide precursor solution comprising an aqueous solution of cerium acetate, cerium chloride, or the like is sprayed into a flame to thermally vaporize the cerium oxide particles. The method of obtaining is mentioned. Among these, cerium oxide particles obtained by spraying in a flame are preferable because of high surface activity and excellent dispersibility.

  In order to improve the dispersion stability in the curable composition, the inorganic oxide particles (A) may be subjected to a surface treatment using a known surface treatment agent such as a silane coupling agent. In the present invention, the inorganic oxide particles (A) not subjected to the surface treatment are cured products obtained from the curable composition even under severe environments such as thermal shock and high temperature and high humidity. The shape is preferable because it hardly changes.

The primary particle diameter of the inorganic oxide particles (A) is usually 1 to 100 nm, preferably 1 to 50 nm. When the primary particle diameter is in the above-described range, a cured product obtained from the curable composition is preferable because the shape hardly changes even under severe environments such as thermal shock and high temperature and high humidity. The primary particle diameter can be measured with a transmission electron microscope.
The number average particle diameter of the inorganic oxide particles (A) contained in the curable composition by the dynamic light scattering method is usually 1 to 100 nm, preferably 1 to 50 nm. When the number average particle diameter is in the above-mentioned range, a cured product obtained from the curable composition is preferable because the shape hardly changes even under severe environments such as thermal shock and high temperature and high humidity.
The specific surface area by gas adsorption method of the inorganic oxide particles (A) is usually ^{10 m} 2 / g or more, preferably 10 to 500 m ² / g, more preferably 50 to 300 m ² / g. When the specific surface area is in the above-described range, a cured product obtained from the curable composition is preferable because the shape hardly changes even under a severe environment such as thermal shock and high temperature and high humidity.

When phosphor particles (E) are contained in the curable composition of the present invention, the number average particle diameter of the inorganic oxide particles (A) by the dynamic light scattering method is the dynamic light of the phosphor particles (E). It is preferably 0.0001 to 0.1 times, more preferably 0.01 to 0.001 times the number average particle size by the scattering method. Within the above range, a cured product obtained from the curable composition is preferable because the shape hardly changes even under severe environments such as thermal shock and high temperature and high humidity.

  Content of an inorganic oxide particle (A) is less than 5 mass parts with respect to 100 mass parts of total amounts of the said polysiloxane (B) and the said polysiloxane (C), Preferably it is 0.01-3 mass. Part, more preferably 0.05 to 1 part by mass. When the content of the inorganic oxide particles (A) is in the above range, the shape of the cured product obtained from the curable composition changes even under severe environments such as thermal shock and high temperature and high humidity. It is preferable because it is difficult. Moreover, it is preferable for LED sealing material use that there is little fall of the light transmittance as it is 0.01-3 mass parts.

1-2. Polysiloxane (B)
The polysiloxane (B) is a polysiloxane having at least two alkenyl groups per molecule and having a silicon atom-bonded aryl group. The polysiloxane (B) is a main component of the composition, and is cured by a hydrosilylation reaction with the polysiloxane (C) to become a main body of the cured product.

The polysiloxane (B) is not particularly limited as long as it can be cured by a hydrosilylation reaction with the polysiloxane (C).
The polysiloxane (B) may be the same compound as the polysiloxane (C). That is, the polysiloxane (B) and the polysiloxane (C) may be a polysiloxane having an alkenyl group and at least two silicon-bonded hydrogen atoms in the same molecule.

Examples of the alkenyl group of the polysiloxane (B) include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a heptenyl group, a hexenyl group, and a cyclohexenyl group. Among these, a vinyl group, an allyl group, and a hexenyl group are preferable.

  The alkenyl group content in the polysiloxane (B) is preferably 3 to 50 mol%, more preferably 5 when the number of all silicon atoms contained in the polysiloxane (B) is 100 mol%. It is -40 mol%, More preferably, it is 10-30 mol%. When the content of the alkenyl group is within the above range, the hydrosilylation reaction between the polysiloxane (B) and the polysiloxane (C) suitably proceeds, and a cured product having high strength can be obtained.

The polysiloxane (B) is a polysiloxane having a silicon atom-bonded aryl group. When the polysiloxane (B) has an aryl group, the cured product obtained from the composition exhibits a characteristic that the shape hardly changes even under a severe environment such as thermal shock and high temperature and high humidity.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

It is preferable that the content ratio of the aryl group is 20 mol% or more with respect to 100 mol% of the total number of silicon atoms contained in the polysiloxane (B). When the content ratio of the aryl group contained in the polysiloxane (B) is in the above range, the cured product obtained from the curable composition has a shape even under a severe environment such as thermal shock and high temperature and high humidity. The characteristic that it is difficult to change is developed.

The amount of the polysiloxane (B1) having an aryl group content of 20 mol% or more with respect to 100 mol% of the total number of silicon atoms contained in the polysiloxane (B) is the polysiloxane (B ) In 100 parts by mass, 50 parts by mass or more, more preferably 70 to 100 parts by mass, and still more preferably 80 to 100 parts by mass. When the amount of the polysiloxane (B1) is within the above range, the cured product obtained from the curable composition is less likely to change its shape even under severe environments such as thermal shock and high temperature and high humidity. Is expressed.

  The polysiloxane (B) is a polysiloxane represented by the following formula (1), and the cured product obtained from the composition changes in shape even under severe environments such as thermal shock and high temperature and high humidity. It is preferable because it is difficult to do.

(In Formula (1), R ¹ may be the same as or different from each other, and is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. 7 to 30 aralkyl groups, or groups in which the hydrogen atoms of these groups are replaced with hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, oxysilanyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 30 carbon atoms . plurality of at least two of R ¹ represents an alkenyl group having 2 to 10 carbon atoms, a plurality of at least one .X hydrogen atoms an aryl group of R ^1, or alkyl of 1 to 3 carbon atoms A and c each independently represents an integer of 1 or more, b, d and f each independently represents an integer of 0 or more, and c / (a + b + c + d) ≧ 0.2.

Examples of the alkyl group having 1 to 10 carbon atoms of R ¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, A cyclooctyl group, a bornyl group, a norbornyl group, an adamantyl group, and the like can be given. Among these, a methyl group is preferable.

Examples of the alkenyl group having 2 to 10 carbon atoms of R ¹ include a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, heptenyl group, hexenyl group, and cyclohexenyl group. be able to. Among these, a vinyl group, an allyl group, and a hexenyl group are preferable.

Examples of the aryl group having 6 to 30 carbon atoms of R ¹ include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among these, a phenyl group is preferable among these.

Examples of the aralkyl group having 7 to 30 carbon atoms of R ¹ include benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group, phenanthrylethyl group, and pyrenylethyl group. .

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, and a tert-butoxy group. Examples of the oxysilanyl group having 2 to 10 carbon atoms include glycidoxyalkyl group such as glycidoxy group and 3-glycidoxypropyl group, 3,4-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 2- ( An epoxycycloalkyl group such as a 3,4-epoxycyclopentyl) ethyl group and a 2- (3,4-epoxycyclohexyl) ethyl group can be exemplified. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

Examples of the alkyl group having 1 to 3 carbon atoms of X include a methyl group, an ethyl group, and an iso-propyl group.
c / (a + b + c + d) ≧ 0.2 or more, preferably 0.5-1. When c / (a + b + c + d) is within the above range, the shape of a cured product obtained from the curable composition is less likely to change even under severe environments such as thermal shock and high temperature and high humidity.

  Even if the polysiloxane (B) has a structural unit represented by the following formula (2) under a severe environment such as thermal shock or high temperature and high humidity, the cured product obtained from the curable composition has a shape. Is preferable because it exhibits the characteristic that it is difficult to change.

(In the formula (2), Ar represents an aryl group having 6 to 30 carbon atoms.)

  Examples of the aryl group having 6 to 30 carbon atoms of Ar include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among these, a phenyl group is preferable among these.

  As a method for producing the polysiloxane (B), JP-A-6-9659, JP-A-2003-183582, JP-A-2007-008996, JP-A-2007-106798, JP-A-2007-169427. And a known method described in JP 2010-059359 A, for example, a method of co-hydrolyzing chlorosilane or alkoxysilane as each unit source in an appropriate synthesis solvent, or a co-hydrolyzate as an alkali metal catalyst. For example, a method of equilibrating reaction may be mentioned.

The content ratio of the polysiloxane (B) contained in the curable composition of the present invention is usually 10 to 90% by mass, more preferably 30 to 80% by mass, and further preferably 50 to 70% by mass.
The weight average molecular weight (Mw) measured by the gel permeation chromatography method of polysiloxane (B) is 100-50,000 normally in polystyrene conversion.
Polysiloxane (B) may be used by 1 type and may use 2 or more types together.

1-3. Polysiloxane (C)
Polysiloxane (C) is a polysiloxane having at least two silicon-bonded hydrogen atoms per molecule. That is, the polysiloxane (C) has at least two Si—H groups (hydrosilyl groups) per molecule. Polysiloxane (C) is a crosslinking agent for polysiloxane (B), and forms a cured product by a hydrosilylation reaction with polysiloxane (B).

  The polysiloxane (C) is not particularly limited as long as it is a polysiloxane having at least two silicon-bonded hydrogen atoms per molecule, which is used as a crosslinking agent in an addition-type curable polysiloxane composition. Can be used.

  Specific examples of the polysiloxane (C) include organohydrogens described in JP2007-327019A, JP2007-008996A, JP2010-229402A, and JP2013-231160A. Examples include polysiloxane.

  Polysiloxane (C) is obtained by reacting an alkoxysilane such as phenyltrimethoxysilane or diphenyldimethoxysilane with a hydrogensiloxane such as 1,1,3,3-tetramethyldisiloxane by a known method. Can do.

  As content of polysiloxane (C) in the curable composition of this invention, the molar ratio of the silicon atom bond hydrogen atom amount in polysiloxane (C) with respect to the amount of alkenyl groups in polysiloxane (B) is 0.1-0.1. 5 is preferable, more preferably 0.5 to 2, and still more preferably 0.7 to 1.4. When the content of the polysiloxane (C) is within the above range, the composition is sufficiently cured, and the obtained cured product has sufficient heat resistance.

The weight average molecular weight (Mw) measured by the gel permeation chromatography method of polysiloxane (C) is 100-50,000 normally in polystyrene conversion.
Polysiloxane (C) may be used alone or in combination of two or more.

1-4. Catalyst for hydrosilylation reaction (D)
The hydrosilylation catalyst (D) is a catalyst for promoting the hydrosilylation reaction. The catalyst for hydrosilylation reaction (D) can be used without particular limitation as long as it is a catalyst used as a catalyst for hydrosilylation reaction in a conventional hydrosilyl polysiloxane composition.

  Specific examples of the hydrosilylation catalyst (D) include a platinum catalyst, a rhodium catalyst, and a palladium catalyst. Among these, a platinum-based catalyst is preferable from the viewpoint of promoting the curing of the present composition. Examples of platinum-based catalysts include platinum-alkenylsiloxane complexes. Examples of the alkenyl siloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable from the viewpoint of the stability of the complex.

The hydrosilylation reaction catalyst (D) in the curable composition of the present invention is an amount in which the hydrosilylation reaction of the polysiloxane (B) and the polysiloxane (C) actually proceeds, usually 0 in the curable composition. Use 0.01 ppm to 10000 ppm.
The hydrosilylation reaction catalyst (D) may be used alone or in combination of two or more.

1-4. Phosphor particles (E)
The phosphor particles (E) are used for wavelength conversion of light-emitting devices such as LEDs. In the curable composition of the present invention, the phosphor particles (E) are contained to form inorganic oxide particles. The dispersion stability of (A) is improved, and the shape of a cured product obtained from the curable composition is less likely to change even under severe environments such as thermal shock and high temperature and high humidity.

The phosphor particles (E) are not particularly limited, and any particles used for wavelength conversion of light emitting devices such as LEDs can be used, and (Sr, Ca) S: Eu, Y ₃ ( Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ A ₁₅ O ₁₂ : Ce, CaGa ₂ S ₄ : Eu, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, SrSiO ₂ N ₂ : Eu, _{CaSiN 2: Eu, Ca 3 Sc} 2 Si 3 O 12: Ce, CaGa 2 S 4: Eu, 2SiO 4: can be mentioned compounds such as Eu.

  The number average particle diameter of the phosphor particles (E) is usually 1 to 30 μm, preferably 5 to 20 μm, as measured by a dynamic light scattering method. When the number average particle diameter of the phosphor particles (E) is in the above range, wavelength conversion of an LED or the like can be efficiently realized by the phosphor particle-containing film formed from the present composition.

The content of the phosphor particles (E) is usually 0 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane (B) and the polysiloxane (C). Part, more preferably 15 to 30 parts by mass. If the content of the phosphor particles (E) is within the above range, the shape of the cured product obtained from the curable composition is less likely to change even under severe environments such as thermal shock and high temperature and high humidity. Become.
A fluorescent substance particle (E) may be used by 1 type, and may use 2 or more types together.

1-5. Other components As long as the object of the present invention is achieved, the curable composition of the present invention can contain, for example, fumed silica, fine particle silica such as quartz powder, ethynylcyclohexanol, cyclo-tetramethyltetravinyl, and the like. Reaction retarders such as tetrasiloxane, diluents such as diphenylbis (dimethylvinylsiloxy) silane, phenyltris (dimethylvinylsiloxy) silane, diphenylbis (dimethylhydroxysiloxy) silane, pigments, flame retardants, heat-resistant agents, antioxidants And components such as a solvent can be contained.

1-6. Production method of curable composition The curable composition of the present invention comprises inorganic oxide particles (A), polysiloxane (B), polysiloxane (C), hydrosilylation catalyst (D) and, if necessary, The phosphor particles (E) and / or the other components can be produced by uniformly mixing them by a known method such as a mixer. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

  The viscosity at 25 ° C. of the curable composition of the present invention is preferably 1 to 100,000 mPa · s, more preferably 10 to 10,000 mPa · s. When the viscosity is within this range, the operability of the composition is improved.

The curable composition of the present invention can be used as one liquid, or can be produced by dividing into two or more liquids, and can be mixed and used at the time of use.

2. Cured product A cured product can be obtained by curing the curable composition of the present invention.
Examples of the method for curing the curable composition of the present invention include a method in which the curable composition is applied on a substrate and then heated at 100 to 180 ° C. for 1 to 13 hours. In addition, a two-stage heat curing method in which the second heating is performed at a temperature higher than the first heating after the first heating can be employed.

  The shape of the cured product of the present invention hardly changes even under severe environments such as thermal shock and high temperature and high humidity. In particular, when the cured product is a thin film, the effect is remarkable if the cured product of the present invention is used. In addition, the said thin film shows a film | membrane with an average film thickness of 1 mm or less.

3. Optical Semiconductor Device An optical semiconductor device of the present invention includes a semiconductor light emitting element and the cured product that covers the semiconductor light emitting element. The optical semiconductor device of the present invention is obtained by coating a semiconductor light emitting element with the curable composition and curing the composition. The method for curing the curable composition is as described above.

Examples of the optical semiconductor device include an LED (Light Emitting Diode) and an LD (Laser Diode).
FIG. 1 is a schematic view of a specific example of the optical semiconductor device of the present invention. The optical semiconductor device 1 includes an electrode 6, a semiconductor light emitting element 2 that is installed on the electrode 6 and electrically connected to the electrode 6 through a wire 7, and a reflector 3 that is disposed so as to accommodate the semiconductor light emitting element 2. The sealing material 4 is filled in the reflector 3 and seals the semiconductor light emitting element 2. The sealing material 4 is obtained by curing the curable composition of the present invention. In the sealing material 4, particles 5 such as silica and phosphor are dispersed.

  FIG. 2 is a schematic view of a specific example of the optical semiconductor device of the present invention. The optical semiconductor device 10 includes a semiconductor light emitting element 12 that is electrically connected to a wiring substrate 11, and a sealing material 13 so as to accommodate the semiconductor light emitting element 12. The sealing material 13 has a fluorescent layer 13a and a transparent layer 13b, and the phosphor layer 13a is obtained by curing the curable composition of the present invention containing the phosphor particles (E), The transparent layer 13b is obtained by curing the curable composition of the present invention that does not contain the phosphor particles (E).

  Since the optical semiconductor device of the present invention includes a cured product whose shape does not easily change even under severe environments such as thermal shock and high temperature and high humidity, the optical semiconductor device can be used under severe environments such as thermal shock and high temperature and high humidity. Even if it exists, it can be used.

1. Synthesis of polysiloxane
1-1. Weight average molecular weight The weight average molecular weight (Mw) of the polysiloxane was measured by gel permeation chromatography (GPC) under the following conditions and determined as a polystyrene equivalent value.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore HXL-M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL

1-2. Synthesis of polysiloxane [Synthesis Example 1]
In a four-necked flask equipped with a stirrer, reflux condenser, inlet, and thermometer, 20 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 120 g of phenyltrimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) propyltrimethoxysilane (6 g), water (15 g), trifluoromethanesulfonic acid (0.1 g), and toluene (500 g) were added and mixed, and the mixture was heated to reflux for 1 hour. After cooling, 2.5 g of a 0.5 wt% aqueous potassium hydroxide solution was added to the reaction solution, and the mixture was heated to reflux for 4 hours, and then excess water was removed by azeotropic dehydration. After cooling, the reaction solution was neutralized with acetic acid and washed with water. Polysiloxane (B1) was obtained by removing the solvent from the reaction solution. The weight average molecular weight of the polysiloxane (B1) was 4,000.

2. Evaluation method The performance of the curable composition was evaluated by the following methods 2-1 and 2-2.
2-1-1. Weight change rate (film thickness 8mm)
After the curable composition was applied on quartz glass, it was heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours to form a cured product having a thickness of 8 mm on the quartz glass. The weight of the cured product before and after storing the cured product at 200 ° C. for 500 hours was measured, and the weight change rate was calculated by the following formula.
[(Weight of cured product before storage) − (weight of cured product after storage)] ÷ (weight of cured product before storage) × 100 (%)

2-1-2. Weight change rate (film thickness 0.7mm)
After the curable composition was applied on quartz glass, it was heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours to form a cured product having a thickness of 0.7 mm on the quartz glass. The weight of the cured product before and after storing this cured product at 200 ° C. for 500 hours or 200 ° C. for 1000 hours was measured, and the weight change rate was calculated by the following formula.
[(Weight of cured product before storage) − (weight of cured product after storage)] ÷ (weight of cured product before storage) × 100 (%)

2-2. Light transmission change rate After the curable composition was applied on quartz glass, it was heated at 100C for 1 hour and then at 150C for 5 hours to form a cured product having a thickness of 1 mm on the quartz glass. The light transmittance at a wavelength of 460 nm before and after storing the cured product at 200 ° C. for 500 hours or at 200 ° C. for 1000 hours was measured, and the light transmission change rate was calculated by the following formula.
[(Light transmittance of cured product before storage) − (Light transmittance of cured product after storage)] ÷ (Light transmittance of cured product before storage) × 100 (%)

3. Evaluation of Curable Composition [Production Examples 1 to 4] Production of Compositions 1 to 4 The components shown in Table 1 are mixed in the blending amounts shown in Table 1 and contain components other than the inorganic oxide particles (A). Compositions (Compositions 1 to 4) were produced. “Parts” in Table 1 indicates parts by mass. The details of each component in Table 1 are as follows.

The following siloxane units are indicated by the following symbols.
M (Vi) :( ViMe ₂ SiO _1/2 )
M (H): (HMe ₂ SiO _1/2 )
D (H) :( HMeSiO _2/2 )
D (Ph) (Ph ₂ SiO _2/2 )
T (Ph) :( PhSiO _3/2 )
(Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.)

B1: Polysiloxane (B1) synthesized in Synthesis Example 1
B2: M (Vi) _0.2 T (Ph) _0.8 (weight average molecular weight is 2,000)
B3: Compound represented by the following formula (3)

C1: Compound represented by the following formula (4)

C2: M (H) _0.5 D (Ph) _0.3 D (H) _0.2 (weight average molecular weight is 1,000)
D1: Complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum metal amount 4% by mass)
E1: Phosphor particles (trade name “Y3957”, manufactured by Intematex)
F1: Ethynylcyclohexanol F2: Silica fine particles (trade name “RX300”, manufactured by Nippon Aerosil Co., Ltd.)

[Experimental Example 1]
In composition 1, 0 part, 0.3 part, 0.5 part, or 1 part of ceria (manufactured by TECNAN, trade name “TECNAPOW-CEO2”, primary particle diameter 5 to 10 nm, specific surface area 85 to 170 m, respectively. ² / g, no surface treatment) was mixed to prepare a curable composition. About these curable compositions, hardened | cured material (film thickness 8mm) was manufactured by the method as described in said "2. Evaluation of a chemical composition", and the weight change rate before and behind 200 degreeC 500 hours storage was evaluated. The results are shown in Table 2.

[Experiment 2]
In composition 2, 0 part or 0.5 part of ceria (trade name “TECNAPOW-CEO2”, primary particle diameter 5 to 10 nm, specific surface area 85 to 170 m ² / g, no surface treatment, manufactured by TECNAN) Were mixed to produce a curable composition. About these curable compositions, hardened | cured material (film thickness 8mm) was manufactured by the method as described in said "2. Evaluation of a chemical composition", and the weight change rate before and behind 200 degreeC 500 hours storage was evaluated. The results are shown in Table 2.

[Experiment 3]
In composition 3, 0 part or 0.3 part of ceria (trade name “TECNAPOW-CEO2”, primary particle diameter 5 to 10 nm, specific surface area 85 to 170 m ² / g, manufactured by TECNAN, no surface treatment), respectively. Were mixed to produce a curable composition. About these curable compositions, hardened | cured material (film thickness 8mm) was manufactured by the method as described in said "2. Evaluation of a chemical composition", and the weight change rate before and behind 200 degreeC 500 hours storage was evaluated. The results are shown in Table 2.

[Experimental Example 4]
In composition 4, 0 part or 0.5 part of ceria (manufactured by TECNAN, trade name “TECNAPOW-CEO2”, primary particle diameter 5 to 10 nm, specific surface area 85 to 170 m ² / g, no surface treatment) Were mixed to produce a curable composition. About these curable compositions, hardened | cured material (film thickness 8mm) was manufactured by the method as described in said "2. Evaluation of a chemical composition", and the weight change rate before and behind 200 degreeC 500 hours storage was evaluated. The results are shown in Table 2.

[Experimental Example 5]
In composition 1, 0 part, 0.3 part, 0.5 part, or 1 part of ceria (manufactured by TECNAN, trade name “TECNAPOW-CEO2”, primary particle diameter 5 to 10 nm, specific surface area 85 to 170 m, respectively. ² / g, no surface treatment) was mixed to prepare a curable composition. About these curable compositions, the hardened | cured material was manufactured by the method as described in said "2. Evaluation of a chemical composition", and the light transmission change rate before and behind 200 degreeC 500 hours storage was evaluated. The results are shown in Table 3.

[Experimental Example 6]
In composition 1, 1 part of ceria (manufactured by TECNAN, trade name “TECNAPOW-CEO2”, primary particle diameter 5 to 10 nm, specific surface area 85 to 170 m ² / g, no surface treatment), or 1 part of zirconia (No. 1) 1 rare element chemical industry make, a brand name "UEP-100", specific surface area 80-120 m < ² > / g, no surface treatment) were mixed, and the curable composition was manufactured. About these curable compositions, hardened | cured material (film thickness 8mm) was manufactured by the method as described in said "2. Evaluation of a chemical composition", and the weight change rate before and behind 200 degreeC 500 hours storage was evaluated. The results are shown in Table 4.

[Experimental Examples 7 and 8]
In composition 4, 0 parts, 0.1 parts, 0.15 parts, or 0.3 parts of ceria (trade name “TECNAPOW-CEO2” manufactured by TECNAN, primary particle diameter of 5 to 10 nm, specific surface area of 85 to 85 parts, respectively. 170 m ² / g, no surface treatment) was mixed with a three roll mill to produce a curable composition. About these curable compositions, hardened | cured material (film thickness 0.7mm) is manufactured by the method as described in the said "2. Evaluation of a chemical composition", 200 degreeC before and after storage for 500 hours (Experimental example 7), and 200 degreeC The weight change rate before and after storage for 1000 hours (Experimental Example 8) was evaluated. The results are shown in Table 5.

[Experimental Examples 9 and 10]
In composition 4, 0 parts, 0.1 parts, 0.15 parts, or 0.3 parts of ceria (trade name “TECNAPOW-CEO2” manufactured by TECNAN, primary particle diameter of 5 to 10 nm, specific surface area of 85 to 85 parts, respectively. 170 m ² / g, no surface treatment) was mixed with a three roll mill to produce a curable composition. About these curable compositions, hardened | cured material (film thickness 1mm) is manufactured by the method as described in the said "2. Evaluation of a chemical composition", before and after 200 degreeC 500-hour storage (Experimental example 9), and 200 degreeC 1000 hours. The light transmission change rate before and after storage (Experimental Example 10) was evaluated. The results are shown in Table 6.

Claims (6)

At least one inorganic oxide particle (A) selected from cerium oxide particles and iron (II) oxide particles (A), a polysiloxane having at least two alkenyl groups per molecule and having silicon-bonded aryl groups ( B) containing a polysiloxane (C) having at least two silicon-bonded hydrogen atoms per molecule, and a catalyst for hydrosilylation reaction (D),
The content of the inorganic oxide particles (A) is less than 5 parts by mass with respect to a total of 100 parts by mass of the polysiloxane (B) and the polysiloxane (C),
The content ratio of the aryl group contained in the polysiloxane (B) is 20 mol% or more with respect to 100 mol% of the total number of silicon atoms contained in the polysiloxane (B). Curable composition. The curable composition according to claim 1, wherein the polysiloxane (B) is a polysiloxane represented by the following formula (1).

(In Formula (1), R ¹ may be the same as or different from each other, and is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. 7 to 30 aralkyl groups, or groups in which the hydrogen atoms of these groups are replaced with hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, oxysilanyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 30 carbon atoms . plurality of at least two of R ¹ represents an alkenyl group having 2 to 10 carbon atoms, a plurality of at least one .X hydrogen atoms an aryl group of R ^1, or alkyl of 1 to 3 carbon atoms A and c each independently represents an integer of 1 or more, b, d and f each independently represents an integer of 0 or more, and c / (a + b + c + d) ≧ 0.2. The curable composition according to claim 1, wherein the polysiloxane (C) has a structural unit represented by the following formula (2).

(In the formula (2), Ar represents an aryl group having 6 to 30 carbon atoms.)   Furthermore, the curable composition as described in any one of Claims 1-3 containing fluorescent substance particle (E). Hardened | cured material obtained by hardening | curing the curable composition as described in any one of Claims 1-4. An optical semiconductor device having the cured product according to claim 5.