JP6010358B2 - Method for preventing or delaying sulfidation of optical semiconductor components - Google Patents

Description

  The present invention relates to an optical semiconductor component composition that can be used as a sealing material and a sealing material for an optical semiconductor component, and a method for producing the same, and further to prevent or delay corrosion of the optical semiconductor component by a sulfur-containing gas. The present invention relates to a method for preventing sulfidation or delaying sulfidation of an optical semiconductor component.

Conventionally, transparent epoxy resin compositions have been widely used to seal optical semiconductor elements such as LEDs. These transparent epoxy resin compositions contain an alicyclic epoxy resin, a curing agent and a curing catalyst, and are used for sealing an optical semiconductor element by a molding method such as casting molding or transfer molding. In general, the epoxy resin composition has excellent handling properties because of the high hardness of the cured product. For example, in a low output white LED sealing application, the required durability can be obtained. Many are used.
However, as LEDs become increasingly brighter and have higher output in recent years, the cured products of conventional transparent epoxy resin compositions can be discolored by continuous use with short-wavelength blue light or ultraviolet light, resulting in a sufficient lifespan. It is difficult. In addition, there is a problem that cracks occur in the cured product due to repeated rapid temperature changes associated with turning on and off.

Recently, in order to solve these problems, instead of epoxy resins, LEDs cured with a resin composition based on a silicone resin having excellent weather resistance have been used. There has been reported an addition-curable silicone composition (Patent Document 1) for protective sealing of optical devices or semiconductor devices by addition reaction of olefins.
However, the silicone resin has high flexibility derived from the silicone skeleton, but has a disadvantage that the hardness of the cured product is low and the surface tends to be sticky, and the strength is low. In addition, the gas permeability is high, and blackening due to sulfuration of Ag used in Ag plating parts of substrates and die attach materials is a problem due to the influence of outgas components from components and gas entering from outside, especially sulfur-containing gas. It has become.
Various anti-sulfurization measures have been taken for electrical / electronic components and optical semiconductor components as anti-sulfurization measures. For example, there have been reports of methods for preventing sulfidation or delaying sulfidation by adding copper powder to a sealing material or sealing material for electric / electronic parts (Patent Documents 2 and 3). However, the copper metal powder is brown, and when it is changed to copper sulfide by a sulfide gas, it becomes a color closer to black, so it is not suitable for a sealing material or a sealing material for optical semiconductor components. In addition, a method for protecting a metal electrode from corrosion due to sulfuration by adding an oxide of a metal element such as a lanthanoid element, yttrium and indium to the silicone rubber composition has been reported (Patent Document 4). However, these metal oxides are not preferable from the viewpoint of color and economy.
In addition, as a method for preventing discoloration of the silver-plated portion of the optical semiconductor and preventing reduction in light reflection efficiency, a method for coating the silver-plated portion with a compound having an electron donating group (Patent Document 5) has been reported. . In addition, it has been reported that silver chloride is generated by a metal chloride catalyst contained in a sealing material or the like, the silver chloride is blackened by a photoreaction, and the silver plating portion is discolored. However, in the method of preventing ionization of silver by coating with a compound having an electron donating group such as imidazoles and benzotriazoles, these compounds become catalyst poisons of the addition reaction of silicone, so that the curing reaction of silicone is inhibited. There is concern about being done.
Similarly, a method of applying a metal having a standard electrode potential smaller than silver to prevent the occurrence of black silver chloride and black silver sulfide (Patent Document 6) has also been proposed. A process of forming a metal film is necessary, and this process requires a coating process on all silver plating parts such as heat sinks and leads, and the process is complicated.
Thus, there is a need for sealing materials and sealing materials that have heat resistance and weather resistance, such as silicone resins, and that have an effect of preventing sulfidation or delaying sulfidation of optical semiconductor components.

JP 2000-198930 A JP 2003-96301 A JP 2006-199752 A JP 2005-113115 A JP 2007-266349 A JP 2008-53564 A

In order to solve these current problems, the present invention has a heat-resistant and UV-resistant light transmittance of a cured product, and can prevent or delay the arrival of a sulfur-containing gas to an optical semiconductor component. And an optical semiconductor component composition that provides a sealing material.
Furthermore, this invention aims at providing the manufacturing method of the said composition, the sealing material and sealing material which consist of the said composition, and sulfidation prevention, and a sulfidation delay method.

As a result of diligent investigations, the present inventors have found that a sealing material and a sealing material of a composition containing a specific thermosetting organosilicon compound and zinc oxide provide an effect of preventing or delaying sulfidation of an optical semiconductor component. And reached the present invention.
That is, the present invention provides the following composition for an optical semiconductor component and a method for producing the same, and a sealing material, a sealing material, and a method for preventing or delaying sulfidation of the optical semiconductor component using the composition.

1. (A) A composition containing a thermosetting organosilicon compound, (B) a hydrosilylation catalyst, and (C) zinc oxide, wherein (A) one or more thermosetting organosilicon compounds are contained in one molecule. The composition for optical semiconductor components which has a unsaturated ring group and one or more silicon atom bond hydrogen atom, and has a heterocyclic ring represented by following formula (1).

2. The (A) thermosetting organosilicon compound comprises (a1) an organic compound having two or more unsaturated bonding groups and a heterocyclic ring represented by the formula (1) in one molecule, and (a2) one molecule. An organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms is reacted at 60 to 120 ° C. in the presence of the (B) hydrosilylation catalyst, and the viscosity at 25 ° C. is 2,000 to 50. 2. The composition for optical semiconductor components as described in 1 above, which is obtained by producing a liquid of 1,000 mPa · s.
3. The average particle diameter of the (C) zinc oxide is 50 nm or less, the content of the (C) zinc oxide in the composition is 0.1 to 50% by mass, and the composition is transparent, 1 Or the composition for optical semiconductor components of 2.
4). The composition for optical semiconductor components according to any one of 1 to 3, further comprising (D) at least one white metal oxide selected from titanium oxide and aluminum oxide.
5. The sealing material or sealing material for optical semiconductor components which consists of a composition for optical semiconductor components in any one of said 1-4.
6). (A) A method for producing a composition containing a thermosetting organosilicon compound, (B) a hydrosilylation catalyst, and (C) zinc oxide, wherein (A) the thermosetting organosilicon compound is (a1) An organic compound having two or more unsaturated bonding groups and a heterocyclic ring represented by the following formula (1) in one molecule; and (a2) an organohydro having two or more silicon-bonded hydrogen atoms in one molecule. Genpolysiloxane is produced such that it reacts at 60 to 120 ° C. in the presence of the hydrosilylation catalyst (B) and becomes a liquid having a viscosity of 2,000 to 50,000 mPa · s at 25 ° C. The manufacturing method of the composition for optical semiconductor components.

7). 5. A method for preventing sulfidation or sulfidation of an optical semiconductor component, wherein the optical semiconductor component is sealed or sealed with a cured product of the composition for optical semiconductor components according to any one of 1 to 4 above.

  The composition for optical semiconductor components of the present invention contains a thermosetting organosilicon compound and zinc oxide. Therefore, the encapsulating material and the sealing material cured product made of the composition for optical semiconductor components have high optical characteristics and high stability, heat resistance and UV transmission resistance, and are suitable for optical semiconductor components using sulfide gas. Sulfidation can be prevented or delayed.

[(A) Thermosetting organosilicon compound]
The (A) thermosetting organosilicon compound of the present invention has one or more unsaturated bond groups and one or more silicon atom-bonded hydrogen atoms in one molecule, and is represented by the following formula (1). Has a heterocyclic ring.

Further, (A) a thermosetting organosilicon compound includes (a1) an organic compound having two or more unsaturated bonding groups and a heterocyclic ring represented by the formula (1) in one molecule, and (a2) one molecule. An organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms therein is reacted in the presence of (B) a hydrosilylation catalyst at 60 to 120 ° C., and the viscosity at 25 ° C. is 2,000 to 50, What is obtained by manufacturing so that it may become a liquid of 000 mPa * s is preferable.
The organic compound (a1) is a heterocyclic-containing compound having two or more unsaturated bond groups capable of hydrosilylation reaction in one molecule. For example, an isocyanuric acid derivative represented by the following chemical formula (1-1) Can be used.

In the above formula (1-1), R ¹ represents a hydrogen atom, an unsaturated hydrocarbon group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a cyclic alkyl group, and each R ² is independently unsaturated. Each represents a hydrocarbon group, which may be the same or different;
The unsaturated hydrocarbon group for R ¹ and R ² preferably has 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, and a butenyl group.

  (A1) Specifically as an organic compound, triallyl isocyanurate, diallyl glycidyl isocyanurate, diallyl methyl isocyanurate, diallyl isocyanurate, tris (2-acryloyloxy) isocyanurate, trimethallyl isocyanurate, triallyl isocyanurate pre Examples include polymers and triallyl cyanuric acid. These can be used alone or in admixture of two or more. Of these, triallyl isocyanurate is preferable from the viewpoint of heat resistance and UV resistance.

The (a2) organohydrogenpolysiloxane contains hydrogen atoms (that is, SiH groups) bonded to two or more silicon atoms in one molecule, preferably bonded to three or more silicon atoms. It contains a hydrogen atom. The (a2) organohydrogenpolysiloxane may be any of linear, branched, or three-dimensional network resin.
Examples of (a2) organohydrogenpolysiloxane include compounds represented by the following formulas (2) to (6).

In the above formulas (2) to (6), each R ³ independently represents a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a phenyl group. Each may be the same or different. Moreover, the repeating unit n or (m + n) shows 1-25, and it is preferable that it is 1-20 from a viewpoint of a viscosity and handling.
Examples of the chain aliphatic hydrocarbon group having 1 to 10 carbon atoms include chain alkyl groups such as methyl group, ethyl group, propyl group, and n-butyl group, and cyclic groups having 3 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

(A2) Organohydrogenpolysiloxanes can be used alone or in admixture of two or more. Further, from the viewpoint of heat resistance and UV transmittance, a compound in which R ³ is a methyl group having 1 carbon is preferable, but from the viewpoint of gas permeability, a compound containing a phenyl group in all or part of R ³ is preferable. Further, from the viewpoint of crosslinking density, it is preferable to have a polyfunctional structure such as formula (5) or a branched structure such as formula (6).

(A2) The organohydrogenpolysiloxane can be obtained by a known method, for example, R ⁴ SiHCl ₂ and R ⁴ ₂ SiHCl (wherein R ⁴ independently does not contain an aliphatic unsaturated bond, unsubstituted Or at least one chlorosilane selected from the group consisting of substituted monovalent hydrocarbon groups). In addition, the organohydrogenpolysiloxane may be one obtained by equilibrating the polysiloxane obtained by cohydrolysis.

The (A) thermosetting organosilicon compound is preferably a liquid having a viscosity at 25 ° C. of 2,000 to 50,000 mPa · s. If the viscosity at 25 ° C. is in the range of 2,000 to 50,000 mPa · s, it is preferable because the handling properties when used as a sealing material or a sealing material are improved.
The viscosity can be measured, for example, using a cone plate viscometer at 25 ° C. according to JIS K5600-2-3.

  In the production of (A) thermosetting organosilicon compound, it is preferable to react 1 to 1.2 equivalents of (a2) organohydrogenpolysiloxane with 1 equivalent of unsaturated bond group of (a1) organic compound. If it is 1 equivalent or more, when it is a cured product (a1) Unreacted residues of unsaturated bond groups of the organic compound can be almost eliminated and there is no fear of coloring, and if it is 1.2 equivalents or less, When this is done, the number of unreacted residues of the SiH group can be kept low. Therefore, by setting it within the above range, there is no possibility that the hardness, heat resistance, and the like when a cured product is deteriorated, the function of the cured product can be improved.

[(B) Hydrosilylation catalyst]
(B) As described above, the hydrosilylation catalyst includes (a1) an organic compound having two or more unsaturated bonding groups and a heterocyclic ring represented by the formula (1) in one molecule, and (a2) one molecule. It is used when hydrosilylation reaction is performed with an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms therein.
(B) As the hydrosilylation catalyst, a catalyst usually used for accelerating the hydrosilylation reaction between a silicon atom bonded with a hydrogen atom and a hydrocarbon having an unsaturated bond can be used. The catalyst is not particularly limited as long as it is a known catalyst used in the above.

As said (B) hydrosilylation catalyst, the transition metal catalyst containing platinum, rhodium, palladium, ruthenium, iridium, etc. can be used, for example, It is preferable to use platinum and a platinum compound especially.
Examples of the platinum compound include hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, and platinum-octylaldehyde / octanol complex. preferable. These can be used alone or in admixture of two or more.

  The amount of (B) hydrosilylation catalyst used is usually preferably in the range of 0.01 to 500 ppm by mass relative to the total mass of (a1) and (a2) as a platinum group metal. More preferably, it is -200 mass ppm. If it is 0.01 mass ppm or more, the reaction can proceed favorably, and if it is 500 mass ppm or less, gelation or coloring during the reaction can be prevented.

(Reaction conditions for hydrosilylation reaction)
(B) In the presence of a hydrosilylation catalyst, a known method can be used for the hydrosilylation reaction between (a1) an organic compound and (a2) an organohydrogenpolysiloxane.
The hydrosilylation reaction can be performed without a solvent, but is preferably performed in a diluting solvent that does not affect the reaction from the viewpoint of reaction control. The diluent solvent is not particularly limited except that it does not have an unsaturated bond group and does not participate in the hydrosilylation reaction.

  Examples of the dilution solvent include alcohols such as methanol, ethanol, 2-propanol, and butanol; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, and ethylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Aliphatic ketones such as cyclopentanone; aromatics such as benzene, toluene, orthoxylene, metaxylene, paraxylene, chlorobenzene and dichlorobenzene; N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl Aliphatic amides such as pyrrolidone; ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. These can be used alone or in admixture of two or more.

  Moreover, about the reaction temperature of hydrosilylation reaction, Preferably it is 60-120 degreeC, More preferably, it is 80-110 degreeC. By setting the temperature at 60 ° C. or higher, the reaction proceeds well and does not significantly slow down. Moreover, control of reaction can be easily performed by setting it as 120 degrees C or less, and it can prevent gelatinizing and coloring.

[(C) Zinc oxide]
(C) Zinc oxide is capable of preventing or delaying the arrival of the sulfur-containing gas to the optical semiconductor component by being sulfided by the sulfur-containing gas. Since it is used as a sealing material, it is suitable as a material that is not colored after being sulfurized by a sulfur-containing gas.
Zinc oxide is transparent to visible light of 380 nm or more. When the particle size is small and the content is small, the composition becomes transparent. When using as a transparent composition, it is preferable that the average particle diameter is 50 nm or less, and the content is 0.1-50 mass% in this composition.

In addition, since zinc oxide can be used as a white inorganic pigment, the composition becomes white when the particle size is large or the content is large. When used as a white composition, the average particle size and shape are not limited, but the average particle size is usually about 0.05 to 5.0 um, preferably 0.1 to 3.0 um, more preferably 0.1. -1.0 um.
The surface treatment is not particularly limited, and various surface treatments may or may not be performed.
Although it does not specifically limit as content of zinc oxide in the case of using as a white composition, Preferably it is 3-200 mass parts with respect to 100 mass parts of (A) thermosetting organosilicon compound, More preferably, it is 5-150. Part by mass, more preferably 10 to 120 parts by mass. If it is 3 parts by mass or more, sufficient whiteness can be obtained, and if it is 200 parts by mass or less, fluidity does not decrease, unfilled or voids are generated during curing, or the mechanical properties of the cured product are deteriorated. There is no fear.

[(D) White metal oxide]
(D) The white metal oxide is at least one selected from titanium oxide and aluminum oxide, and can be used as a white pigment when used as a white sealing material with improved reflectivity. (C) Oxidation By using it mixed with zinc, the reflectance of the cured product of the composition is dramatically improved. Various others can be used for the same purpose, and examples include magnesium oxide and hollow glass particles.
Among various white pigments, titanium oxide and aluminum oxide are preferable from the viewpoints of easy handling, availability, and cost. In particular, titanium oxide is more preferable because of its excellent hiding power as a white pigment.

Various titanium oxides can be used and may be an anatase type or a rutile type, but a rutile type is preferred in that it has no photocatalytic action and the composition tends to be stable. Although the average particle diameter and shape of titanium oxide are not limited, the average particle diameter is usually about 0.05 to 5.0 μm, preferably 0.1 to 3.0 μm, more preferably 0.1 to 1.0 μm.
The surface treatment of titanium oxide is not particularly limited, and various surface treatments may or may not be performed.

  (D) The content of the white metal oxide is not particularly limited, but is preferably 3 to 200 parts by weight, more preferably 5 to 150 parts by weight, with respect to 100 parts by weight of the (A) thermosetting organosilicon compound. More preferably, it is 10-120 mass parts. If it is 3 parts by mass or more, sufficient whiteness can be obtained, and if it is 200 parts by mass or less, fluidity does not decrease, unfilled or voids are generated during curing, or the mechanical properties of the cured product are deteriorated. There is no fear.

[Antioxidant]
The composition for optical semiconductor components of the present invention comprises (A) a thermosetting organosilicon compound, (B) a hydrosilylation catalyst, (C) zinc oxide as essential components, and (D) titanium oxide or aluminum oxide as necessary. A white metal oxide selected more is added, and a sealing material or a sealing material can be obtained.
In addition to the above, these compositions can contain various additives such as antioxidants and fillers. By adding an antioxidant, coloring of the cured product when exposed to a high temperature environment for a long time can be reduced. As the antioxidant, various known compounds such as hindered phenol antioxidants and thioether compound antioxidants can be applied.

  Examples of the hindered phenol antioxidant include 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, and stearyl-β- (3, Monophenols such as 5-di-tert-butyl-4,4-dihydroxyphenyl) propionate; 2,2-methylenebis (4-methyl-6-tert-butylphenol), 2,2-methylenebis (4-ethyl-6) Bisphenols such as -tert-butylphenol) and 4,4'-thiobis (3-methyl-6-tert-butylphenol); 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- Chill-4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionate] methane, and the like.

  Examples of the thioether compound-based antioxidant include dilauryl 3,3′-dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-dilauryl 3,3′-thiodipropionate, distearyl 3, 3'-dilauryl 3.3'-thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate), etc. are mentioned.

  Moreover, antioxidant containing a phosphorus atom can also be used together. For example, triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10- Examples thereof include dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

These antioxidants can be used alone or in admixture of two or more.
The addition amount of the antioxidant is not particularly limited, but is preferably 0.001 to 20% by mass, more preferably 0.01 to 5% by mass with respect to the entire composition. Addition in the range of 0.001 to 20% by mass is preferable for reducing coloration.

[Composition for optical semiconductor components]
The composition for optical semiconductor components of the present invention comprises (A) a thermosetting organosilicon compound, (B) a hydrosilylation catalyst, and (C) zinc oxide, and (D) a white metal oxide, an antioxidant, if necessary. Furthermore, it can be produced by mixing other additives. Moreover, the manufacturing method of the composition for optical semiconductor components of this invention has the characteristics in the manufacturing method of (A) thermosetting organosilicon compound mentioned above.
In the production of the composition for optical semiconductor components of the present invention, (A) a thermosetting organosilicon compound obtained by the above-described method for producing a thermosetting organosilicon compound, (B) a hydrosilylation catalyst, and Is mixed with the above (C) zinc oxide, (D) white metal oxide, antioxidant, and other additives.

  Examples of the other additives include dyes, pigments, surfactants, oxide nanoparticles, nitride nanoparticles, antifouling agents, metal fillers, and heat resistance agents. Moreover, if it is a grade which does not impair hardening, it is also possible to use a solvent, a reactive diluent, etc., and to adjust a viscosity and improve handling property.

[Method of preventing or delaying sulfidation of sealing material, sealing material and optical semiconductor component]
The present invention also provides an optical semiconductor component sealing material or sealing material comprising the aforementioned optical semiconductor component composition.
The LED that can use the sealing material and the sealing material for the optical semiconductor component is, for example, made of not only a recent LED having a high light emission efficiency and a short wavelength, but also a compound semiconductor GaP, a compound semiconductor GaAs, and a compound semiconductor GaN. Red LEDs, green LEDs, and yellow LEDs. The above-mentioned composition can be used for sealing existing LEDs, and is optimal for high-efficiency LEDs having a light emission efficiency of 80 lm / W or more at a wavelength of blue or ultraviolet light that has been recently developed.
Furthermore, (C) zinc oxide contained in the composition for optical semiconductor components can be prevented or delayed from reaching the optical semiconductor component of the sulfur-containing gas by being sulfurized by the sulfur-containing gas as described above. is there. Thus, the present invention can also provide a method for preventing or delaying sulfidation of an optical semiconductor component, in which the optical semiconductor component is sealed or sealed with a cured product of the composition for optical semiconductor components.

  The embodiments of the present invention will be described by way of examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Synthesis Example 1]
(A) Synthesis of thermosetting organosilicon compound (resin A) In a 500 ml four-separable flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube and a stirring blade, triallyl isocyanurate of (a1) [ 38.0 parts by mass and 50 parts by mass of toluene were added to the product, and the mixture was stirred at room temperature. (B) platinum divinyltetramethyldisiloxane complex xylene solution [trade name: S1P6831.2, Gelest, Inc. 0.075 parts by mass] was added and heated to 80 ° C. using a mantle heater. The organohydrogenpolysiloxane having a SiH group (a2) dissolved in 100 parts by mass of toluene (trade name: HMS-301, Gelest, Inc.). 112.0 parts by mass, molecular weight 1900-2000 (catalog value)] was added dropwise to the reaction solution over 1 hour. The temperature of the reaction solution was raised to 100 ° C. and stirred as it was for 5 hours. The solvent of the obtained reaction mixture was distilled off under reduced pressure to obtain a thermosetting organosilicon compound (resin A).
The obtained resin was a colorless and transparent liquid, and the viscosity at 25 ° C. was 6,500 mPa · s.

[Synthesis Example 2]
Organosiloxane having a vinyl group (trade name: DMS-VO3, Geiest, Inc.) was added to a 500 ml four-separable flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube and a stirring blade. 75.8 parts by mass, molecular weight 500 (catalog value)] and 75 parts by mass of toluene were added and stirred at room temperature. (B) Platinum divinyltetramethyldisiloxane complex xylene solution [trade name: SIP6831.2, Gelest, Inc. 0.075 parts by mass] was added and heated to 80 ° C. using a mantle heater. The organohydrogenpolysiloxane having the SiH group (a2) dissolved in 75 parts by mass of toluene (trade name: HMS-301, Gelest, Inc.). 74.2 parts by mass, molecular weight 1900-2000 (catalog value)] was added dropwise to the reaction solution over 1 hour, the temperature of the reaction solution was raised to 100 ° C., and the mixture was stirred as it was for 5 hours. The solvent of the mixture was distilled off under reduced pressure to obtain a thermosetting silicone resin (resin B).
The obtained resin was a colorless and transparent liquid, and the viscosity at 25 ° C. was 12,000 mPa · s.

[Examples 1-3, Comparative Examples 1-2]
Each component was mixed at the compounding ratio shown in Table 1 to obtain a resin composition. The following physical property evaluation was performed about the obtained resin composition.

(1) Cured product characteristics The above resin composition is poured into a cell prepared by sandwiching a 2 mm thick silicone rubber sheet as a spacer between two glass plates, and heated at 120 ° C. for 2 hours and at 150 ° C. for 5 hours. It hardened by carrying out and produced the plate-shaped hardened | cured material of thickness 2mm.
The physical properties of the produced plate-like cured product were evaluated by the following methods, and the results are shown in Table 1.
(1-1) Appearance The plate-like cured product was visually observed and evaluated for color and transparency.
(1-2) Transmittance (initial value), reflectance (initial value)
Using a UV-visible spectrophotometer (V-570) manufactured by JASCO Corporation, the light transmittance (transparent material) or reflectance (white material) at 460 nm of the plate-like cured product was measured. The evaluation criteria are as follows.
O: 80% or more, Δ: 70 to 79%, x: less than 70% (1-3) UV light transmittance, reflectance A plate using a cut filter that cuts light with a wavelength of 300 nm or less with a UV irradiation device After the shaped cured product was irradiated with UV light for 100 hours, the light transmittance (transparent material) or reflectance (white material) at 460 nm was measured. The evaluation criteria are as follows.
O: 80% or more, Δ: 70 to 79%, x: less than 70% (1-4) heat-resistant light transmittance, reflectance 460 nm light transmittance after placing the plate-like cured product in an oven at 150 ° C. for 200 hours The rate (transparent material) or reflectance (white material) was measured. The evaluation criteria are as follows.
O: 80% or more, Δ: 70 to 79%, x: less than 70% (1-5) Crack resistance A plate-like cured product having a size of 4 cm × 1 cm is placed in an oven at 300 ° C. for 5 minutes and heated. The cured product was taken out of the oven and simultaneously placed in 10 ° C. cold water to evaluate whether cracks occurred. The evaluation criteria are as follows.
○: No cracking occurred, ×: Cracking occurred (1-6) Surface stickiness When the plate-shaped cured product is put in a polyethylene bag at room temperature and brought into contact with the surface, does the plate-shaped cured product stick to the bag? I evaluated it. The evaluation criteria are as follows.
○: Not sticky, ×: Sticky

(2) Corrosion test A metal substrate obtained by silver-plating a copper plate is placed on a glass substrate, and the resin composition shown in Table 1 is applied on the glass substrate to a thickness of 0.5 mm from the top to 150 ° C. for 2 hours, 150 hours. An evaluation sample was produced by heating at 5 ° C. for 5 hours to cure.
This evaluation sample was placed in a sealable container having a volume of 500 ml, and then 50 mg of sulfur powder was placed in the container. This container was put into a dryer at 150 ° C. and left for the time (1 h, 2 h) shown in Table 1 to evaluate the occurrence of corrosion on the surface of the metal substrate. The evaluation criteria are as follows.
◯: No discoloration, △: Slight discoloration, ×: Discoloration

  The cured product of the composition for optical semiconductor components of the present invention has high optical properties and high stability, has heat resistance and UV transmittance, and contains zinc oxide, so that it can be sulfided by a sulfide gas. Since it can be prevented or delayed, it is useful as a sealing material and a sealing material for optical semiconductor components.

Claims (3)

(A) A composition containing a thermosetting organosilicon compound, (B) a hydrosilylation catalyst, and (C) zinc oxide, wherein (A) one or more thermosetting organosilicon compounds are contained in one molecule. The optical semiconductor component is sealed with a cured product of the composition for optical semiconductor components having an unsaturated bond group of 1 and one or more silicon-bonded hydrogen atoms and a heterocyclic ring represented by the following formula (1) : Method for preventing or delaying sulfidation of optical semiconductor components.
The average particle diameter of the (C) zinc oxide is 50 nm or less, and the content of the (C) zinc oxide in the composition is 0.1 to 50% by mass, and the composition is transparent. 2. A method for preventing sulfidation or delaying sulfidation of an optical semiconductor component according to 1 . The method for preventing or delaying sulfidation of an optical semiconductor component according to claim 1, further comprising (D) at least one white metal oxide selected from titanium oxide and aluminum oxide .