JP2007291274A - Sealant for optical semiconductor device and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealant for optical semiconductor devices which is highly transparent, does not cause discoloration due to the heat generated and light emitted from the light emitting devices, is excellent in heat resistance and light resistance, has a good adhesion to the housing materials, improves the refractive indices and increases the efficiency of the light transmission through the sealant on optical semiconductor devices. <P>SOLUTION: The sealant for optical semiconductor devices contains a thermally curable compound having not less than one cyclic ether-containing group in the molecule and a curing agent reactive with the cyclic ether-containing group. The thermally curable compound has a structural unit expressed by general formula (1) and/or a structural unit expressed by general formula (2) and/or a structural unit expressed by general formula (3) and/or a structural unit expressed by general formula (4). M<SP>1</SP>O<SB>4/2</SB>: (1) M<SP>2</SP>O<SB>3/2</SB>: (2) R<SP>1</SP>SiO<SB>3/2</SB>: (3) R<SP>2</SP>R<SP>3</SP>SiO<SB>2/2</SB>: (4). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention has high transparency, no discoloration due to heat generation or light emission of the light emitting element, excellent heat resistance and light resistance, excellent adhesion to housing materials, etc., and can further improve the refractive index, and emit light. The present invention relates to an encapsulant for optical semiconductor elements capable of increasing light extraction efficiency when the element is encapsulated, and an optical semiconductor element using the encapsulant for optical semiconductor elements.

Light-emitting elements such as light-emitting diodes (LEDs) are usually sealed with a sealant because their light-emitting characteristics rapidly deteriorate due to moisture in the atmosphere or floating dust when they come into direct contact with the atmosphere. It has a structure. As a resin constituting a sealant for sealing such a light emitting element, epoxy resin such as bisphenol type epoxy resin and alicyclic epoxy resin is used because of its high adhesive strength and excellent mechanical durability. (For example, refer to Patent Document 1).

By the way, in recent years, LEDs have come to be used for applications that require high brightness, such as automotive headlights and lighting. Therefore, the sealant that seals the light emitting element has a heat generation during lighting. In addition to high heat resistance that can withstand an increase in the amount of light, high light resistance that prevents light deterioration associated with higher brightness has been required. However, it is difficult to say that a conventional sealant made of an epoxy resin has sufficient heat resistance and light resistance, and is made of an epoxy resin in applications requiring high brightness such as automotive headlights and lighting. There was a problem that the sealant may not be able to cope.

Further, a conventional sealant made of an epoxy resin has low transmittance for light having a short wavelength in a blue to ultraviolet region, and may cause coloration due to light deterioration or heat deterioration. There was a problem that it could not be used for sealants such as light-emitting diodes, ultraviolet light-emitting diodes, and white light-emitting diodes combining these with phosphors.

On the other hand, in place of epoxy resin, a method is known in which a silicone resin having a high transmittance for light having a short wavelength in the blue to ultraviolet region is used as a sealant for sealing a light emitting element of an LED (for example, Patent Document 2). reference).
However, since the silicone resin is generally soft and has surface tackiness, foreign substances are likely to adhere to the surface of the light emitting element, and the light emitting surface may be damaged during sealing. In contrast, silicone resins with increased crosslink density are inferior in mechanical strength, have insufficient adhesion to housing materials that enclose light-emitting elements, and have high moisture permeability. There has been a problem in that the light emitting characteristics of the light emitting element are deteriorated. Furthermore, the silicone resin has a problem that the light extraction efficiency is poor when the light emitting element is sealed with a low refractive index.
JP 2003-277473 A JP 2002-314142 A

In view of the above-mentioned present situation, the present invention has high transparency, no discoloration due to heat generation or light emission of a light emitting element, excellent heat resistance and light resistance, excellent adhesion to a housing material, and further improves the refractive index. An optical semiconductor element encapsulant that can increase the light extraction efficiency when the light emitting element is encapsulated, and an optical semiconductor element using the optical semiconductor element encapsulant With the goal.

The present invention is an optical semiconductor element sealing agent comprising a thermosetting compound having at least one cyclic ether-containing group in a molecule and a thermosetting agent capable of reacting with the cyclic ether-containing group, The thermosetting compound includes a structural unit represented by the following general formula (1) and / or a structural unit represented by the general formula (2), a structural unit represented by the following general formula (3), and / or a general one. The sealing agent for optical semiconductor elements which has a structural unit represented by Formula (4).
M ¹ O _4/2 (1)
M ² O _3/2 (2)
R ¹ SiO _3/2 (3)
R ² R ³ SiO _2/2 (4)
In the above formula, M ¹ represents titanium or zirconium, M ² represents aluminum, R ¹ and R ² represent cyclic ether-containing groups, and R ³ is the same as R ² or linear Represents a branched or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

Further, the present invention is a sealant for a semiconductor element comprising a thermosetting compound having one or more cyclic ether-containing groups in the molecule, and a thermosetting agent capable of reacting with the cyclic ether-containing group, The thermosetting compound comprises an alkoxysilane compound having one or more cyclic ether-containing groups in the molecule, a titanium alkoxide compound, a zirconium alkoxide compound, an aluminum alkoxide compound, a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. An encapsulant for optical semiconductor elements obtained by condensing a mixture containing at least one compound selected from the above.
The present invention is described in detail below.

As a result of intensive studies, the present inventors can react with a thermosetting resin having a specific structure having one or more cyclic ether-containing groups, silicon and other metal elements in the molecule, and the cyclic ether-containing group. Sealant containing thermosetting agent has high transparency to short wavelength light from blue to ultraviolet region, no heat generation or discoloration due to light emission of sealing light emitting element, excellent heat resistance and light resistance, light emitting diode When used as a sealing agent for sealing a light emitting element of an optical semiconductor element, etc., it has excellent adhesion to a housing material or the like enclosing the light emitting element, can further improve the refractive index, and seal the light emitting element. The inventors have found that the light extraction efficiency can be increased when stopped, and have completed the present invention.

The sealing agent for optical semiconductor elements of this invention contains the thermosetting compound which has 1 or more of cyclic ether containing groups in a molecule | numerator.
The cyclic ether-containing group is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Of these, a glycidyl group and / or an epoxycyclohexyl group are preferable.

The glycidyl group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl Group, 4-glycidoxybutyl group and the like.
Moreover, it does not specifically limit as said epoxy cyclohexyl group, For example, 2- (3,4-epoxy cyclohexyl) ethyl group, 3- (3,4- epoxy cyclohexyl) propyl group, etc. are mentioned.

In the said thermosetting compound, as content of the said cyclic ether containing group, a preferable minimum is 0.1 mol% and a preferable upper limit is 50 mol%. When the content is less than 0.1 mol%, the reactivity between the thermosetting compound and the thermosetting agent described later is remarkably lowered, and the curability of the encapsulant for optical semiconductor elements of the present invention may be insufficient. is there. When it exceeds 50 mol%, the cyclic ether-containing group that does not participate in the reaction between the thermosetting compound silicone resin and the thermosetting agent increases, and the heat resistance of the encapsulant for optical semiconductor elements of the present invention may decrease. . A more preferred lower limit is 5 mol%, and a more preferred upper limit is 30 mol%.
In addition, in this specification, content of the said cyclic ether containing group means the quantity of the said cyclic ether containing group with respect to all the organic groups couple | bonded with the silicon atom which comprises the said thermosetting compound.

In the encapsulant for optical semiconductor elements of the present invention, the thermosetting compound includes a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2) and the general formula. The structural unit represented by (3) and / or the structural unit represented by the general formula (4).
Since the thermosetting resin has the above-described structure, the encapsulant for optical semiconductor elements of the present invention is highly permeable to light having a short wavelength in the blue to ultraviolet region, and is generated by heat generation or light emission of the light emitting element to be sealed. There is no discoloration and excellent heat resistance and light resistance, and when the light emitting element of an optical semiconductor element such as a light emitting diode is sealed, the optical semiconductor element has excellent adhesion to a housing material or the like.

In the general formulas (1) to (4), M ¹ represents titanium or zirconium, M ² represents aluminum, R ¹ and R ² represent cyclic ether-containing groups, and R ³ represents R ^2. Or a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the thermosetting compound having the above structure, when the proportions of the structural units represented by the general formulas (1), (2), (3) and (4) are a, b, c and d, respectively, When the ratio a of the structural unit represented by the formula (1) is b / (a + b + c + d)> 0, the lower limit of a / (a + b + c + d) is preferably 0, and b / (a + b + c + d) = 0 In this case, the lower limit of a / (a + b + c + d) is preferably 0.05. The upper limit of a / (a + b + c + d) is preferably 0.3. If it exceeds 0.3, it may be difficult for the encapsulant for optical semiconductor elements of the present invention to maintain an appropriate viscosity as an encapsulant, or the cured product may become brittle.

In addition, when the ratio b of the structural unit represented by the general formula (2) is a / (a + b + c + d)> 0, the lower limit of b / (a + b + c + d) is preferably 0, and a / (a + b + c + d) ) = 0, the lower limit of b / (a + b + c + d) is preferably 0.1. Moreover, it is preferable that the upper limit of b / (a + b + c + d) is 0.5. If it exceeds 0.5, it may be difficult for the encapsulant for optical semiconductor elements of the present invention to maintain an appropriate viscosity as an encapsulant, or the cured product may become brittle.

In addition, when the ratio c of the structural unit represented by the general formula (3) is d / (a + b + c + d)> 0, the lower limit of c / (a + b + c + d) is preferably 0, and d / (a + b + c + d). ) = 0, the lower limit of c / (a + b + c + d) is preferably 0.05. Moreover, it is preferable that the upper limit of c / (a + b + c + d) is 0.4. If it exceeds 0.4, it becomes difficult for the encapsulant for optical semiconductor elements of the present invention to maintain an appropriate viscosity as an encapsulant, the cured product becomes brittle, or the heat resistance decreases. Sometimes.

Furthermore, the ratio d of the structural unit represented by the general formula (4) is preferably 0 when d / (a + b + c + d) is greater than 0 when c / (a + b + c + d)> 0, and c / (a + b + c + d). ) = 0, the lower limit of d / (a + b + c + d) is preferably 0.1. Moreover, it is preferable that the upper limit of c / (a + b + c + d) is 0.4. If it exceeds 0.4, the heat resistance of the encapsulant for optical semiconductor elements of the present invention may deteriorate.

In the encapsulant for optical semiconductor elements of the present invention, the thermosetting compound includes a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), and In addition to the structural unit represented by the general formula (3) and / or the structural unit represented by the general formula (4), the structural unit represented by the following general formula (5) and / or the general formula (6) It is preferable to have a structural unit represented by

R ⁴ SiO _3/2 (5)
R ⁵ R ⁶ SiO _2/2 (6)

In the above formulas (5) and (6), R ^{4 to} R ⁶ may be the same or different and each represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. .

The curable resin compound is a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), a structural unit represented by the general formula (3) and / or In addition to the structural unit represented by the general formula (4), the present invention includes the structural unit represented by the general formula (5) and / or the structural unit represented by the general formula (6). The heat resistance of the cured product of the encapsulant for optical semiconductor elements is improved, and cracks and the like are not generated in a thermal cycle or the like.

Moreover, when the said thermosetting compound contains the structural unit represented by the structural unit represented by the said General formula (5) and / or General formula (6), when these ratios are set to e and f, respectively, Regarding the ratio e of the structural unit represented by the general formula (5) and the ratio f of the structural unit represented by the general formula (6), the lower limit of (e + f) / (a + b + c + d + e + f) is 0.2, the upper limit. Preferably satisfies the relationship of 0.9. When 0.9 is exceeded, the hardened | cured material of the sealing agent for optical semiconductor elements of this invention may become weak. A more preferred lower limit is 0.3, and a more preferred upper limit is 0.8.

Moreover, in the sealing agent for optical semiconductor elements of this invention, the said thermosetting compound may have units other than the structural unit represented by the said General formula (1)-(6) as needed. Good.

In the encapsulant for optical semiconductor elements of the present invention, the preferable lower limit of the number average molecular weight (Mn) of the thermosetting compound is 1000, and the preferable upper limit is 50,000. If it is less than 1000, the amount of volatile components increases at the time of thermosetting, and the film loss of the sealant may increase. If it exceeds 50,000, viscosity adjustment as a sealant becomes difficult. A more preferred lower limit is 3000, and a more preferred upper limit is 15000.
In the present specification, the number average molecular weight (Mn) is a value obtained using polystyrene as a standard using gel permeation chromatography (GPC), and is a measuring device manufactured by Waters (column: manufactured by Showa Denko KK). It means a value measured using Shodex GPC LF-804 (length: 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene.

The thermosetting compound having such a structure includes, for example, an alkoxysilane compound having one or more cyclic ether-containing groups in the molecule, a titanium alkoxide compound, a zirconium alkoxide compound, an aluminum alkoxide compound, a titanium chelate compound, a zirconium chelate compound, and It can be produced by condensing a mixture containing at least one compound selected from the group consisting of aluminum chelate compounds (hereinafter also referred to as a metal compound according to the present invention). An encapsulant for optical semiconductor elements, in which the thermosetting compound is produced by the above method, is also one aspect of the present invention.

The alkoxysilane compound having one or more cyclic ether-containing groups in the molecule is hydrolyzed and condensed together with the metal compound according to the present invention, whereby the structural unit represented by the general formula (3) and / or It is a compound which becomes a structural unit represented by the general formula (4). Of the alkoxysilane compounds having one or more cyclic ether-containing groups in the molecule, the constituent unit represented by the general formula (3) is not particularly limited. The trialkoxysilane having a cyclic ether-containing group is preferable, although it is not particularly limited as a constituent unit represented by the general formula (4).

Specific examples of the trialkoxysilane having a cyclic ether-containing group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, etc. Is mentioned.

Specific examples of the organodialkoxysilane having a cyclic ether-containing group include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidide. Xylpropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (Methyl) dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxysilane, and the like. These may be used independently and 2 or more types may be used together.

The metal compound according to the present invention is hydrolyzed and condensed together with an alkoxysilane compound having one or more cyclic ether-containing groups in the above molecule, whereby the structural unit represented by the above general formula (1) and / or Or it is a compound used as the structural unit represented by General formula (2). Examples of the structural unit represented by the general formula (1) among the metal compounds described above include titanium alkoxide compounds, zirconium alkoxide compounds, titanium chelate compounds, and zirconium chelate compounds. Examples of the structural unit represented by 2) include a zirconium alkoxide compound and an aluminum chelate compound.

The titanium alkoxide compound is not particularly limited. For example, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-i-butoxytitanium, tetra-sec-butoxy. Examples thereof include titanium and tetra-t-butoxy titanium. These may be used independently and 2 or more types may be used together.

The zirconium alkoxide compound is not particularly limited. For example, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetra-i-propoxyzirconium, tetra-n-butoxyzirconium, tetra-i-butoxyzirconium, tetra-sec-butoxy Zirconium, tetra-t-butoxyzirconium and the like can be mentioned. These may be used independently and 2 or more types may be used together.

The titanium chelate compound is not particularly limited. For example, triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxymono (acetylacetonato) titanium. , Tri-n-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonate) ) Titanium, di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy・ Bis (acetylacetonate) titanium, -T-butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, mono-n-propoxy tris (acetylacetonato) titanium, mono-i-propoxy tris (acetylacetonate) Titanium, mono-n-butoxy tris (acetylacetonato) titanium, mono-sec-butoxy tris (acetylacetonato) titanium, mono-t-butoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonate) Titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl aceto) acetate Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl aceto) Acetate) titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t- Butoxy bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono -N-Butoxy Lith (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) Examples include tris (ethyl acetoacetate) titanium, bis (acetylacetonato) bis (ethyl acetoacetate) titanium, tris (acetylacetonate) mono (ethyl acetoacetate) titanium, and the like. These may be used independently and 2 or more types may be used together.

The zirconium chelate compound is not particularly limited. For example, triethoxy mono (acetylacetonato) zirconium, tri-n-propoxymono (acetylacetonato) zirconium, tri-i-propoxymono (acetylacetonato) zirconium. , Tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxymono (acetylacetonato) zirconium, diethoxybis (acetylacetonate) ) Zirconium, di-n-propoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium , Di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetyl) Acetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t -Butoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoa) Tate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t- Butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di- n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoeth Xy-tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) Zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonato) tris (ethyl acetoacetate) Zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, etc. It is. These may be used independently and 2 or more types may be used together.

The aluminum alkoxide compound is not particularly limited, and examples thereof include triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, tri-i-butoxyaluminum, and tri-sec-butoxy. Examples thereof include aluminum and tri-t-butoxyaluminum. These may be used independently and 2 or more types may be used together.

The aluminum chelate compound is not particularly limited, and examples thereof include diethoxy mono (acetylacetonato) aluminum, di-n-propoxy mono (acetylacetonato) aluminum, and di-i-propoxy mono (acetylacetonato) aluminum. , Di-n-butoxy mono (acetylacetonato) aluminum, di-sec-butoxy mono (acetylacetonato) aluminum, di-t-butoxy mono (acetylacetonato) aluminum, ethoxy bis (acetylacetonate) ) Aluminum, n-propoxy bis (acetylacetonato) aluminum, i-propoxy bis (acetylacetonato) aluminum, n-butoxy bis (acetylacetonato) aluminum, sec-butoxy Su (acetylacetonato) aluminum, t-butoxy bis (acetylacetonato) aluminum, diethoxymono (ethylacetoacetate) aluminum, di-n-propoxymono (ethylacetoacetate) aluminum, di-i-propoxy Mono (ethyl acetoacetate) aluminum, di-n-butoxy mono (ethyl acetoacetate) aluminum, di-sec-butoxy mono (ethyl acetoacetate) aluminum, di-t-butoxy mono (ethyl acetoacetate) aluminum, Ethoxy bis (ethyl acetoacetate) aluminum, n-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, n-butoxy bis ( Chill acetoacetate) aluminum, sec- butoxy bis (ethylacetoacetate) aluminum, t-butoxy-bis (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, and the like. These may be used independently and 2 or more types may be used together.

In addition, when the alkoxysilane compound having one or more cyclic ether-containing groups in the molecule and the metal compound according to the present invention are subjected to a condensation reaction, the alkoxysilane compound having one or more cyclic ether-containing groups in the molecule. It is preferable to blend other alkoxysilane compounds or partial hydrolysates thereof different from the above.

The other alkoxysilane compounds are not particularly limited. For example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3, 3, 3 -Trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethoxy Examples include diethoxysilane.

Examples of a method for producing the thermosetting compound by condensing a mixture containing an alkoxysilane compound having one or more cyclic ether-containing groups in the molecule and the metal compound according to the present invention include, for example, the intramolecular And a method in which an alkoxysilane compound having one or more cyclic ether-containing groups and the metal compound according to the present invention are hydrolyzed and condensed in the presence of water and a catalyst.

When the thermosetting compound is produced by the above method, the amount of water added is not particularly limited, and the alkoxysilane compound having one or more cyclic ether-containing groups in the molecule and the silicon atom in the metal compound of the present invention The amount is not particularly limited as long as the amount of the alkoxy group bonded to the titanium atom or the like can be sufficiently hydrolyzed.

The catalyst is not particularly limited, and examples thereof include a basic catalyst and an acid catalyst. Of these, a basic catalyst is preferably used.

The basic catalyst is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; sodium-t-butoxide, potassium-t-butoxide, cesium-t-butoxide. Alkali metal alkoxides such as sodium silanolate compounds, potassium silanolate compounds, alkali metal silanol compounds such as cesium silanolate compounds, and the like. Of these, potassium-based catalysts and cesium-based catalysts are preferred.

The acidic catalyst is not particularly limited, and examples thereof include inorganic acids such as phosphoric acid, boric acid, and carbonic acid; formic acid, acetic acid, propionic acid, lactic acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, Examples thereof include organic acids such as succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid, and acid anhydrides or derivatives thereof.

The addition amount of the catalyst is not particularly limited, but the preferred lower limit is 10 ppm and the preferred upper limit with respect to the total amount of the alkoxysilane compound having one or more cyclic ether-containing groups in the molecule and the metal compound according to the present invention. Is 10,000 ppm. Within this range, the curable compound to be produced can be prevented from precipitating or gelling during the reaction. A more preferred lower limit is 100 ppm, and a more preferred upper limit is 1000 ppm. The basic catalyst may be added as it is, or may be added after dissolving in a small amount of water or an alkoxysilane compound having one or more cyclic ether-containing groups in the molecule.

When the alkoxysilane compound having one or more cyclic ether-containing groups in the molecule and the metal compound according to the present invention are condensed, the thermosetting compound to be synthesized can be prevented from being precipitated from the reaction system, and Since water and free water due to the condensation reaction can be removed by azeotropic distillation, it is preferable to use an organic solvent.
Examples of the organic solvent include aromatic organic solvents such as toluene and xylene; ketone organic solvents such as acetone and methyl isobutyl ketone; aliphatic organic solvents such as hexane, heptane and octane. Of these, aromatic organic solvents are preferably used.

Although it does not specifically limit as reaction temperature at the time of the said condensation reaction, A preferable minimum is 40 degreeC and a preferable upper limit is 200 degreeC, A more preferable minimum is 50 degreeC and a more preferable upper limit is 150 degreeC. Moreover, when using the said organic solvent, the said condensation reaction can be easily performed at reflux temperature by using what has a boiling point in the range of 40-200 degreeC as this organic solvent.

The sealing agent for optical semiconductor elements of this invention contains the thermosetting agent which can react with the said cyclic ether containing group.
The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group of the thermosetting compound. For example, ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N- Aliphatic amines such as ethylaminopiperazine, isophoronediamine, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenol Methane, aromatic amines such as 4,4'-diaminodiphenol ether, mercaptopropionic acid esters, mercaptans such as terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ) Methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, bromine Phenolic resins such as bisphenol A novolac, polyols hydrogenated aromatic rings of these phenolic resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydride Phthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic acid anhydrides, cycloaliphatic acid anhydrides such as methyl-norbornane-2,3-dicarboxylic acid anhydride, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 2 -Obtained by reaction of imidazoles such as methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole and salts thereof, the above aliphatic amines, aromatic amines, and / or imidazoles with epoxy resins. Amine adducts, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1,8-dia Bicyclo [5.4.0] undecene tertiary amines such as -7, organic phosphines such as triphenylphosphine, dicyandiamide, and the like. Among them, acid anhydrides such as alicyclic acid anhydrides and aromatic acid anhydrides are preferable, more preferably alicyclic acid anhydrides, and particularly preferably methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride. These thermosetting agents may be used independently and 2 or more types may be used together.

The blending amount of the thermosetting agent is not particularly limited, but the preferred lower limit is 1 part by weight and the preferred upper limit is 200 parts by weight with respect to 100 parts by weight of the silicone resin. Within this range, the encapsulant for optical semiconductor elements of the present invention sufficiently undergoes a crosslinking reaction, is excellent in heat resistance and light resistance, and has a sufficiently low moisture permeability. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 120 parts by weight.

It is preferable that the sealing agent for optical semiconductor elements of this invention contains a hardening accelerator further.
The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; and third compounds such as 1,8-diazabicyclo (5,4,0) undecene-7. Phosphines such as triphenylphosphine; phosphonium salts such as triphenylphosphonium bromide; tins such as aminotriazoles, tin octylate and dibutyltin dilaurate, zincs such as zinc octylate, aluminum, And metal catalysts such as acetylacetonate such as chromium, cobalt, and zirconium. These hardening accelerators may be used independently and may use 2 or more types together.

Although it does not specifically limit as a compounding quantity of the said hardening accelerator, A preferable minimum is 0.01 weight part with respect to 100 weight part of said thermosetting compounds, and a preferable upper limit is 5 weight part. If it is less than 0.01 part by weight, the effect of adding the curing accelerator cannot be obtained, and if it exceeds 5 parts by weight, the coloring of the cured product of the encapsulant for optical semiconductor elements of the present invention, heat resistance, The light resistance is significantly reduced. A more preferred lower limit is 0.05 parts by weight, and a more preferred upper limit is 1.5 parts by weight.

The encapsulant for optical semiconductor elements of the present invention may contain a coupling agent for imparting adhesion.
The coupling agent is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycosoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, Examples thereof include silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane. These coupling agents may be used independently and 2 or more types may be used together.

As a blending ratio of the coupling agent, a preferable lower limit is 0.1 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the thermosetting compound. If the amount is less than 0.1 part by weight, the effect of coupling agent may not be sufficiently exhibited. If the amount exceeds 5 parts by weight, the excess coupling agent may volatilize, resulting in film loss.

The encapsulant for optical semiconductor elements of the present invention may contain an antioxidant in order to improve heat resistance.
The antioxidant is not particularly limited. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-t) Phenol-type antioxidants such as -butylphenol), triphenyl phosphite, tridecyl phosphite, nonyl diphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene, 9,10 -Phosphorous antioxidants such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dilauryl-3,3'-thiodipropionate, ditride Sulfur-based antioxidants such as sil-3,3′-thiodipropionate, [4,4′-thiobis (3-methyl-6-tert-butylphenyl)]-bis (alkylthiopropionate), and other oxidations Examples of the inhibitor include metal antioxidants such as fullerene, iron, zinc and nickel. These antioxidants may be used alone or in combination of two or more.

As a blending ratio of the antioxidant, a preferable lower limit is 0.001 part by weight and a preferable upper limit is 2 parts by weight with respect to 100 parts by weight of the thermosetting compound. If the amount is less than 0.001 part by weight, the effect of blending the antioxidant may not be sufficiently exhibited. If the amount exceeds 2 parts by weight, the antioxidant will volatilize, causing film loss or the like. It may become brittle.

In addition, the encapsulant for optical semiconductor elements of the present invention may contain silica fine powder, high molecular weight silicone resin, or the like in order to adjust the viscosity. In particular, the silica fine powder not only has a thickening action but also acts as a thixotropic agent, so that the fluidity control of the encapsulant for optical semiconductor elements of the present invention and the effect of preventing sedimentation of the phosphor also occur. Is more preferable.

Although it does not specifically limit as an average particle diameter of the said silica fine powder, A preferable upper limit is 100 nm. When it exceeds 100 nm, the transparency of the encapsulant for optical semiconductor elements of the present invention may be lowered.

Moreover, the said silica fine powder has a preferable minimum of a BET specific surface area of 30 m < ² > / g, and a preferable upper limit of 500 m < ² > / g on performance. If it is less than 30 m ² / g, the thickening effect and the thixotropy improving effect are insufficient, and if it exceeds 500 m ² / g, the silica fine powder is strongly aggregated and difficult to disperse.

Examples of such silica fine powder include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 ( Specific surface area: 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g), Aerosil OX50 (specific surface area: 50 m ² / g), Aerosil TT600 (specific surface area) : 200 m ² / g), Aerosil R972 (specific surface area: 110 m ² / g), Aerosil R974 (specific surface area: 170 m ² / g), Aerosil R202 (specific surface area: 100 m ² / g), Aerosil R812 (specific surface area: 260 m) ² / g) Aerosil R812S (specific surface ^{area: 220m 2 / g), Aerosil} R805 ( specific surface ^{area: 150m 2 / g), RY200} ( specific surface ^{area: 100m 2 / g), RX200} ( specific surface area: 140m ² / g) (both Nippon Aerosil Etc.).

The encapsulant for optical semiconductor elements of the present invention contains additives such as an antifoaming agent, a colorant, a phosphor, a modifying agent, a leveling agent, a light diffusing agent, and a heat conductive filler as necessary. Also good.

The preferable lower limit of the refractive index of the encapsulant for optical semiconductor elements of the present invention is 1.50. If it is less than 1.50, the light extraction property of the optical semiconductor element using the optical semiconductor element sealing agent of the present invention may be insufficient.

Although it does not specifically limit as a viscosity of the sealing agent for optical semiconductor elements of this invention, A preferable minimum is 500 mPa * s and a preferable upper limit is 50,000 mPa * s. If it is less than 500 mPa · s, liquid dripping occurs and the optical semiconductor element may not be sealed. If it exceeds 50,000 mPa · s, the optical semiconductor element may not be uniformly and accurately sealed. A more preferred lower limit is 1000 mPa · s, and a more preferred upper limit is 10,000 mPa · s.
In addition, in this specification, the said viscosity is the value measured on 25 degreeC and 5 rpm conditions using the E-type viscosity meter (the Toki Sangyo company make, TV-22 type | mold).

The encapsulant for optical semiconductor elements of the present invention preferably has an initial light transmittance of 90% or more. If it is less than 90%, the optical characteristics of the optical semiconductor element using the optical semiconductor element sealing agent of the present invention will be insufficient. In addition, the said initial light transmittance uses the hardened | cured material of thickness 1mm which hardened | cured the sealing agent for optical semiconductor elements of this invention, and the transmittance | permeability of the light of wavelength 400nm is "U-4000" by Hitachi, Ltd. It is the value measured using.

Moreover, it is preferable that the sealing agent for optical semiconductor elements of this invention has the decreasing rate of the light transmittance after a light resistance test of less than 10%. If it is 10% or more, the optical characteristics of the optical semiconductor element using the optical semiconductor element sealing agent of the present invention will be insufficient. The light resistance test described above is a 1 mm thick cured product obtained by curing the sealant for optical semiconductor elements of the present invention, and a high-pressure mercury lamp fitted with a filter that cuts light having a wavelength of 340 nm or less. The light transmittance after the light resistance test is a test of irradiating cm ² , and the light transmittance at a wavelength of 400 nm is measured using “U-4000” manufactured by Hitachi, Ltd., using the cured product after the light resistance test. Measured value.

Moreover, it is preferable that the sealing agent for optical semiconductor elements of this invention has the decreasing rate of the light transmittance after a heat resistance test of less than 10. If it is 10% or more, the optical characteristics of the optical semiconductor element using the optical semiconductor element sealing agent of the present invention will be insufficient. The heat resistance test is a test in which a 1 mm-thick cured product obtained by curing the sealant for optical semiconductor elements of the present invention is left in an oven at 150 ° C. for 500 hours, and the light beam after the heat resistance test. The transmittance is a value obtained by measuring the transmittance of light having a wavelength of 400 nm using “U-4000” manufactured by Hitachi, Ltd., using the cured product after the heat resistance test.

The encapsulant for optical semiconductor elements of the present invention contains a thermosetting compound having one or more cyclic ether-containing groups in the molecule, and a thermosetting agent capable of reacting with the cyclic ether-containing group, and the above thermosetting The structural compound represented by the general formula (1) and / or the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3) and / or the general formula (3) 4), it has high transparency, no heat generation of the light emitting element or discoloration due to light emission, and excellent heat resistance and light resistance, as well as excellent adhesion to the housing material. Further, the refractive index can be improved, the light extraction efficiency can be increased when the light emitting element is sealed, and it can be suitably used for sealing a light emitting element such as a short wavelength light emitting diode. .

The method for producing the sealant for optical semiconductor elements of the present invention is not particularly limited. For example, using a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll, a bead mill, Or the method etc. which mix each predetermined amount, such as the thermosetting compound mentioned above, a thermosetting agent, a hardening accelerator, and an additive, are mentioned under heating.

An optical semiconductor element can be manufactured by sealing a light emitting element using the sealing agent for optical semiconductor elements of this invention.
The light emitting element is not particularly limited. For example, when the optical semiconductor element is a light emitting diode, for example, a semiconductor material stacked on a substrate can be used. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.
Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. In addition, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the buffer layer include GaN and AlN.

The method for laminating the semiconductor material on the substrate is not particularly limited, and examples thereof include MOCVD, HDVPE, and liquid phase growth.
Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. Moreover, it can also be set as a single or multiple quantum well structure.

An optical semiconductor element can be manufactured by sealing the light emitting element using the optical semiconductor element sealing agent of the present invention, but at this time, another sealing agent may be used in combination. In this case, after sealing the light emitting element with the sealant for optical semiconductor elements of the present invention, the periphery thereof may be sealed with the other sealant, and the light emitting element may be sealed with the other sealant. Then, the periphery thereof may be sealed with the optical semiconductor sealing agent of the present invention.
The other sealing agent is not particularly limited, and examples thereof include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass.

The method for sealing the light emitting element with the encapsulant for optical semiconductor elements of the present invention is not particularly limited. For example, the encapsulant for optical semiconductor elements of the present invention is pre-injected into a mold frame, and light is emitted there. Examples include a method of immersing a lead frame or the like to which the element is fixed and then curing, a method of injecting the curing agent for an optical semiconductor element of the present invention into a mold in which a light emitting element is inserted, and the like.
Examples of the method for injecting the sealant for optical semiconductor elements of the present invention include injection by a dispenser, transfer molding, injection molding and the like. Furthermore, as another sealing method, the sealing agent for optical semiconductor elements of the present invention is dropped on the light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, and the light emitting element is formed at the bottom. The method etc. which inject | pour the sealing agent for optical semiconductor elements of this invention with a dispenser etc. to the arrange | positioned cup etc., and make it harden | cure.
Furthermore, the encapsulant for optical semiconductor elements of the present invention can also be used as a die bond material for fixing the light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.

In the encapsulant for optical semiconductor elements of the present invention, the thermosetting resin has one or more cyclic ether-containing groups in the molecule, and the structural unit represented by the general formula (1) and / or the general formula (2 ), And the structural unit represented by the general formula (3) and / or the structural unit represented by the general formula (4), it is suitable for light having a short wavelength in the blue to ultraviolet region. High transparency, no heat generation or discoloration due to light emission of the light emitting element to be sealed, excellent heat resistance and light resistance, and when the light emitting element of an optical semiconductor element such as a light emitting diode is sealed, the housing of the optical semiconductor element Excellent adhesion to materials and the like. Further, the refractive index can be improved, the light extraction efficiency can be increased when the light emitting element is sealed, and it can be suitably used for sealing a light emitting element such as a short wavelength light emitting diode. .
The housing material is not particularly limited, and examples thereof include conventionally known materials made of aluminum, polyphthalamide resin (PPA), polybutylene terephthalate resin (PBT), or the like.
An optical semiconductor element using the encapsulant for optical semiconductor elements of the present invention is also one aspect of the present invention.

Specific examples of the optical semiconductor element of the present invention include a light emitting diode, a semiconductor laser, and a photocoupler. Such an optical semiconductor element of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copy machine, a vehicle measuring instrument light source, a signal light, a display light, a display device, and a planar light emission. It can be suitably used for body light sources, displays, decorations, various lights, switching elements and the like.

According to the present invention, the transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, the heat resistance and the light resistance are excellent, the adhesiveness to the housing material, etc. is excellent, and the refractive index can be improved. It is possible to provide an optical semiconductor element encapsulant that can increase the light extraction efficiency when the light emitting element is encapsulated, and an optical semiconductor element using the optical semiconductor element encapsulant.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples.

(Synthesis Example 1)
In a separable flask equipped with a 2000 mL thermometer and a dropping device, 650 g of dimethyldimethoxysilane, 150 g of 3-glycidoxypropylmethyldimethoxysilane, and 100 g of tetrakis (acetylacetonate) titanium were added and stirred at 50 ° C.
Into this, potassium hydroxide (1.9 g) / water (250 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid 2.1g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer was obtained.
The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer A. The molecular weight of the polymer A is Mn = 3100, Mw = 5400, and the epoxy equivalent is 790 g / eq. Met.

The molecular weight was stirred until tetrahydrofuran (1 mL) was added and dissolved in polymer A (10 mg), and a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK) Measurement temperature: 40 ° C., flow rate: 1 ml / min, solvent: tetrahydrofuran, standard substance: polystyrene) was used for GPC measurement. Moreover, the epoxy equivalent was calculated | required based on JISK-7236.

(Synthesis Example 2)
In a separable flask equipped with a 2000 mL thermometer and a dropping device, 650 g of dimethyldimethoxysilane, 150 g of 3-glycidoxypropylmethyldimethoxysilane, and 100 g of tributoxymono (acetylacetonato) zirconium were added and stirred at 50 ° C.
Into this, potassium hydroxide (1.9 g) / water (250 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours.
The acetic acid 2.1g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer was obtained.
The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer B. The molecular weight of the polymer B is Mn = 5300, Mw = 10200, and the epoxy equivalent is 770 g / eq. Met. The molecular weight and epoxy equivalent of polymer B were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
In a separable flask with a 2000 mL thermometer and a dropping device, 600 g of dimethyldimethoxysilane, 150 g of 3-glycidoxypropylmethyldimethoxysilane, and 150 g of tri-n-butoxyaluminum were added and stirred at 50 ° C.
Into this, potassium hydroxide (1.9 g) / water (250 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours.
The acetic acid 2.1g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer was obtained.
The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer C. The molecular weight of the polymer C is Mn = 2300, Mw = 4700, and the epoxy equivalent is 790 g / eq. Met. The molecular weight and epoxy equivalent of polymer C were determined in the same manner as in Synthesis Example 1.

Example 1
Polymer A 100 g, Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd.) 25 g, U-CAT SA 102 (curing accelerator, manufactured by San Apro) 0.5 g are mixed and defoamed for an optical semiconductor element. A sealant was obtained. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 2)
Except having used the polymer B instead of the polymer A, it carried out similarly to Example 1, and obtained the sealing compound for optical semiconductor elements, and its hardened | cured material.

(Example 3)
Except having used polymer C instead of polymer A, it carried out similarly to Example 1, and obtained the sealing agent for optical semiconductor elements, and its hardened | cured material.

(Comparative Example 1)
Celoxide 2021 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, 50 g), YX-8000 (hydrogenated bisphenol A epoxy resin, manufactured by Japan Epoxy Resin, 50 g), Ricacid MH-700G (manufactured by Nippon Nippon Chemical Co., Ltd., 100 g) U-CAT SA 102 (manufactured by Sun Apro, 0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 2)
VDT-431 (polysiloxane having a vinyl group, manufactured by Gelest, 45 g), HMS-031 (organohydrogenpolysiloxane, manufactured by Gelest, 55 g), octyl alcohol-modified solution of chloroplatinic acid (Pt concentration: 2% by weight, 0.05 g) was added and mixed and defoamed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled into a mold and cured at 100 ° C. for 3 hours and 150 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Evaluation)
The following evaluation was performed about the sealing agent produced in Examples 1-3 and Comparative Examples 1 and 2, and its hardened | cured material.

(1) Initial light transmittance A light transmittance of 400 nm was measured using a U-4000 manufactured by Hitachi, Ltd. using a cured product having a thickness of 1 mm.

(2) Light transmittance after light resistance test A cured product with a thickness of 1 mm is attached to a high-pressure mercury lamp with a filter that cuts 340 nm or less, irradiated with 100 J / cm ² , and a light transmittance of 400 nm is made by Hitachi, Ltd. U -4000 was used for the measurement. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 10%: ○, when less than 10-40%: Δ, when 40 or more: x.

(3) Light transmittance after heat resistance test A cured product having a thickness of 1 mm was left in an oven at 150 ° C. for 500 hours, and a light transmittance of 400 nm was measured using U-4000 manufactured by Hitachi, Ltd. In Table 1, when the decrease rate of light transmittance from the initial stage is less than 10%: ○, when less than 10-40%: Δ, when 40% or more: x.

(4) Adhesion test A sealant for optical semiconductor is applied to aluminum, polyphthalamide resin (PPA), polybutylene terephthalate resin (PBT), and cured at 100 ° C. × 3 hours, 130 ° C. × 3 hours to form a thin film. It produced and the adhesiveness test was done using the gobang eye adhesion test method. In Table 1, when the number of peels was 0: ◯, when the number of peels 1 to 70: Δ, and when the number of peels 71 to 100: x.

(5) Using the refractive index cured product, measurement was performed using a refractometer (Abbe type) at a d-line (587.6 nm) of a helium light source and a temperature of 20 ° C.

According to the present invention, the transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, the heat resistance and the light resistance are excellent, the adhesion to the housing material is excellent, and the refractive index can be further improved, It is possible to provide an optical semiconductor element sealing agent capable of increasing light extraction efficiency when the light emitting element is sealed, and an optical semiconductor element using the optical semiconductor element sealing agent.

Claims (9)

An encapsulant for an optical semiconductor element comprising a thermosetting compound having one or more cyclic ether-containing groups in a molecule and a thermosetting agent capable of reacting with the cyclic ether-containing group,
The thermosetting compound includes a structural unit represented by the following general formula (1) and / or a structural unit represented by the general formula (2), a structural unit represented by the following general formula (3), and / or It has a structural unit represented by General formula (4), The sealing compound for optical semiconductor elements characterized by the above-mentioned.
M ¹ O _4/2 (1)
M ² O _3/2 (2)
R ¹ SiO _3/2 (3)
R ² R ³ SiO _2/2 (4)
In the above formula, M ¹ represents titanium or zirconium, M ² represents aluminum, R ¹ and R ² represent cyclic ether-containing groups, and R ³ is the same as R ² or linear Represents a branched or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The thermosetting compound further comprises a structural unit represented by the following general formula (5) and / or a structural unit represented by the following general formula (6). Sealant.
R ⁴ SiO _3/2 (5)
R ⁵ R ⁶ SiO _2/2 (6)
R ⁴ to R ⁶ may each have the same or different and represent a linear or branched hydrocarbon or a fluorinated compound having 1 to 8 carbon atoms. A sealant for a semiconductor element comprising a thermosetting compound having at least one cyclic ether-containing group in a molecule and a thermosetting agent capable of reacting with the cyclic ether-containing group,
The thermosetting compound comprises an alkoxysilane compound having one or more cyclic ether-containing groups in the molecule, a titanium alkoxide compound, a zirconium alkoxide compound, an aluminum alkoxide compound, a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. An encapsulant for optical semiconductor elements, which is obtained by condensing a mixture containing at least one compound selected from the above. 4. The encapsulant for optical semiconductor elements according to claim 3, wherein the mixture further contains another alkoxysilane compound different from the alkoxysilane compound having at least one cyclic ether-containing group in the molecule. The encapsulant for optical semiconductor elements according to claim 1, 2, 3 or 4, wherein the cyclic ether-containing group is a glycidyl group and / or an epoxycyclohexyl group. The number average molecular weight of a thermosetting compound is 1000-50,000, The sealing agent for optical semiconductor elements of Claim 1, 2, 3, 4 or 5 characterized by the above-mentioned. The encapsulant for optical semiconductor elements according to claim 1, 2, 3, 4, 5, or 6, wherein the thermosetting agent is an acid anhydride. Furthermore, the hardening accelerator is contained, The sealing agent for optical semiconductor elements of Claim 1, 2, 3, 4, 5, 6 or 7 characterized by the above-mentioned. An optical semiconductor element comprising the optical semiconductor sealant according to claim 1, 2, 3, 4, 5, 6, 7 or 8.