JP2009102574A - Curable composition for optical semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing agent for an optical semiconductor element, from which a cured material can be obtained which is excellent in transparency, heat resistance, light resistance and adhesion to a housing material and is neither cracked nor exfoliated even when a sudden thermal change is given to the cured material by a heat cycle and to provide the optical semiconductor element made using the sealing agent. <P>SOLUTION: The curable composition for the optical semiconductor element includes; a silicone resin having a cyclic ether-containing group in the molecule thereof; a compound having at least one radical-polymerizable unsaturated group and at least one silane group in the molecule thereof; a curing agent reacting with the cyclic ether-containing group; and a polymerization initiator reacting with the radical-polymerizable unsaturated group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention provides an optical semiconductor element that is excellent in transparency, heat resistance, light resistance, and adhesion to a housing material, and can obtain a cured product that does not generate cracks or peeling even when subjected to a rapid thermal change due to a thermal cycle. The present invention relates to a sealing agent for use and an optical semiconductor element using the same.

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 the sealant for sealing such a light emitting element, since it has low moisture permeability, high adhesion, and excellent mechanical durability, it is possible to use bisphenol type epoxy resin, alicyclic epoxy resin, etc. Epoxy resins have been used (see, for example, Patent Document 1).

However, in recent years, LEDs have come to be used for applications that require high brightness such as automotive headlights and lighting, and as a result, the sealant that seals the light emitting element has high brightness. In addition to the high light resistance that prevents the accompanying light deterioration, extremely high heat resistance that can withstand the increase in the amount of heat generated during lighting has been required.
However, the conventional sealant made of epoxy resin has advantages such as high adhesion and low moisture permeability, but it is difficult to say that it has sufficient heat resistance and light resistance. In applications that require high brightness, such as, there is a problem of coloring.

On the other hand, instead of an epoxy resin, a method is known in which a silicone resin having a high transmittance for light of a short wavelength in the blue to ultraviolet region and excellent in heat resistance and light resistance is used as a sealing agent for sealing an LED light emitting element. (For example, refer to Patent Document 2).

However, since the silicone resin-based sealant has surface tackiness, there is a problem that foreign substances are easily attached to the light emitting surface and the light emitting surface is easily damaged. When the light emitting surface is damaged in this way, cracks are generated from that portion, or the luminance is remarkably lowered due to the damage.

For this, a method using a silicone resin-based sealant with an increased crosslinking density has been studied. However, increasing the crosslink density can eliminate surface tackiness and prevent adhesion of foreign materials and damage to the light emitting surface. However, mechanical strength and adhesion are significantly reduced. Or peeling from the housing material. In addition, since the silicone resin has a high moisture permeability, the light emitting characteristics of the light emitting element may deteriorate when used for a long time.

In order to solve these problems, a method of supplementing the drawbacks of each resin by using a silicone resin and an epoxy resin in combination has been studied. For example, Patent Document 3 discloses a thermosetting composition for sealing a light-emitting element, in which a modified polysiloxane having two or more epoxy groups in one molecule and, if necessary, an epoxy resin are blended. Thus, the thermosetting composition for light emitting element sealing obtained by mix | blending an epoxy resin can exhibit the outstanding adhesiveness.
However, the composition in which the modified polysiloxane and the epoxy resin are blended cannot obtain sufficient transparency, and the cured product obtained does not sufficiently improve the problem of mechanical strength and is inferior in crack resistance. It was a problem that left much problems. This is presumably because the compatibility between the modified polysiloxane and the epoxy resin is low.
Therefore, as a resin composition for optical semiconductors, particularly a resin composition that can be used for sealing applications, it has excellent transparency, heat resistance, light resistance, adhesion, and excellent crack resistance. Was demanded.
JP 2003-277473 A JP 2002-314142 A JP 2004-289102 A

In view of the above situation, the present invention provides a cured product that is excellent in transparency, heat resistance, light resistance, and adhesion to a housing material, and that does not generate cracks or peeling even when subjected to a rapid thermal change due to a thermal cycle. An object of the present invention is to provide an encapsulant for optical semiconductor elements that can be used, and an optical semiconductor element using the same.

The present invention relates to a silicone resin having a cyclic ether-containing group in the molecule (hereinafter also simply referred to as a silicone resin), a compound having at least one radical-polymerizable unsaturated group and at least one silane group in the molecule ( Hereinafter, also referred to as a radical polymerizable compound), a curing agent that reacts with the cyclic ether-containing group (hereinafter also simply referred to as a curing agent), and a polymerization initiator that reacts with the radical polymerizable unsaturated group (hereinafter simply referred to as polymerization). And a curable composition for optical semiconductor elements.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have obtained a cured product having high transparency and the like by using a composition containing a silicone resin, a radical polymerizable compound, a curing agent, and a polymerization initiator. At the same time, it has been found that high crack resistance is exhibited, and the present invention has been completed.
Since the radically polymerizable compound has a silane group, it has extremely high compatibility with the silicone resin, and the radically polymerizable compound can be finely dispersed in the curable composition for optical semiconductor elements of the present invention. In the curable composition for optical semiconductor elements of the present invention, the radically polymerizable compound forms a polymer with a polymerization initiator in such a finely dispersed state. Curing progresses. Here, since the polymerization reaction rate of the radical polymerizable compound is remarkably faster than the curing reaction rate of the silicone resin, a polymer of the radical polymerizable compound is surely formed in the obtained cured product. Therefore, in the obtained cured product, the polymer of the radical polymerizable compound is present in a uniformly dispersed state. That is, in the obtained cured product, the polymer of the radical polymerizable compound and the silicone resin form a sea-island structure microscopically. Therefore, high crack resistance can be exhibited by the polymer of the radically polymerizable compound existing in a uniformly dispersed state in the obtained cured product as a stress relaxation agent. Further, in the obtained cured product, the polymer of the radical polymerizable compound is present in a uniformly dispersed state, so that high transparency and the like that are derived from the silicone resin are not hindered.

The curable composition for optical semiconductor elements of the present invention contains a silicone resin having a cyclic ether-containing group in the molecule.
In the thermosetting composition for optical semiconductors of the present invention, the silicone resin is not particularly limited as long as it is a silicone resin having one or more cyclic ether-containing groups in the molecule. What contains the resin component represented by Formula (1) is preferable.

In the general formula (1), a, b, c and d are a / (a + b + c + d) = 0 to 0.2, b / (a + b + c + d) = 0.3 to 1.0, c / (a + b + c + d) = 0 to 0.5, d / (a + b + c + d) = 0 to 0.3 is satisfied, and R ^{1 to} R ⁶ each represent at least one cyclic ether-containing group, and R ^{1 to} R ⁶ other than the cyclic ether-containing group Represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different.

When the silicone resin contains a resin component having an average composition formula represented by the general formula (1), the thermosetting composition for optical semiconductors according to the present invention is suitable for light having a short wavelength in the blue to ultraviolet region. Light-emitting element for optical semiconductor elements such as light-emitting diodes, which has high transparency and is excellent in heat resistance and light resistance without causing heat generation or discoloration due to light emission of the light-emitting element to be sealed when used as a sealing agent for optical semiconductor elements. When this is sealed, the optical semiconductor element has excellent adhesion to the housing material or the like.
In addition, the said average composition formula is represented with the said Formula (1) not only when the thermosetting composition for optical semiconductors of this invention contains only the resin component represented by the said Formula (1). In the case of a mixture containing resin components having various structures, the average of the composition of the resin components contained also means the case represented by the above formula (1).

In the general formula (1), at least one of R ^{1 to} R ⁶ represents a cyclic ether-containing group.
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.

The epoxycyclohexyl group is not particularly limited, and examples thereof include 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, and the like.

In the silicone resin, the preferable lower limit of the content of the cyclic ether-containing group is 0.1 mol%, and the preferable upper limit is 50 mol%. When the content is less than 0.1 mol%, the reactivity between the silicone resin and the thermosetting agent described later is remarkably lowered, and the curability of the thermosetting composition for optical semiconductors of the present invention may be insufficient. . If it exceeds 50 mol%, the cyclic ether-containing group not involved in the reaction between the silicone resin and the thermosetting agent increases, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention may be lowered. 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 contained in the average composition of the said silicone resin component.

In the silicone resin represented by the general formula (1), R ^{1 to} R ⁶ other than the cyclic ether-containing group are linear, branched or cyclic hydrocarbons having 1 to 8 carbon atoms or fluorinated products thereof. To express.

The linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n- Hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, phenyl group Etc.

In the silicone resin represented by the general formula (1), the structural unit represented by (R ⁴ R ⁵ SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following general formula (1-2): That is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxyl group or an alkoxy group.
(R ⁴ R ⁵ SiXO _1/2 ) (1-2)
In the general formula (1-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the silicone resin represented by the general formula (1), the structural unit represented by (R ⁶ SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following general formula (1-3) Or a structure represented by (1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxyl group or an alkoxy group, or silicon in a trifunctional structural unit It includes a structure in which one of oxygen atoms bonded to an atom constitutes a hydroxyl group or an alkoxy group.

(R ⁶ SiX ₂ O _1/2 ) (1-3)
(R ⁶ SiXO _2/2 ) (1-4)
In the general formulas (1-3) and (1-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the silicone resin represented by the general formula (1), the structural unit represented by (SiO _4/2 ) (hereinafter, also referred to as tetrafunctional structural unit) is represented by the following general formula (1-5), ( 1-6) or (1-7), that is, a structure in which three or two oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit constitute a hydroxyl group or an alkoxy group, or four It includes a structure in which one of oxygen atoms bonded to a silicon atom in the functional structural unit constitutes a hydroxyl group or an alkoxy group.
(SiX ₃ O _1/2 ) (1-5)
_{(SiX 2 O 2/2) (1-6} )
(SiXO _3/2 ) (1-7)
In the general formulas (1-5), (1-6), and (1-7), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. To express.

In the general formulas (1-2) to (1-7), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and an n-propoxy group. N-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

In the general formula (1), a is a numerical value that satisfies the relationship that the lower limit of a / (a + b + c + d) is 0 and the upper limit is 0.2. If it exceeds 0.2, the heat resistance of the thermosetting composition for optical semiconductors of the present invention may deteriorate.

In the general formula (1), b is a numerical value that satisfies the relationship that the lower limit of b / (a + b + c + d) is 0.3 and the upper limit is 1.0. If it is less than 0.3, the cured product of the thermosetting composition for optical semiconductors of the present invention becomes too hard, and when used as a semiconductor peripheral member such as a sealant, die bonding material, underfill, etc. Cracks or the like may occur between the adherends.

In the general formula (1), c is a numerical value that satisfies the relationship that c / (a + b + c + d) has a lower limit of 0 and an upper limit of 0.5. If it exceeds 0.5, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention.

Furthermore, in the general formula (1), d is a numerical value that satisfies the relationship that the lower limit of d / (a + b + c + d) is 0 and the upper limit is 0.3. If it exceeds 0.3, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention.

When the ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed on the silicone resin represented by the general formula (1) based on tetramethylsilane (hereinafter referred to as TMS), there is a slight variation depending on the type of substituent. Although seen, a peak corresponding to the structural unit represented by (R ¹ R ² R ³ SiO _1/2 ) _a in the general formula (1) appears in the vicinity of +10 to 0 ppm, and ( R ⁴ R ⁵ SiO _2/2 ) Each peak corresponding to the bifunctional structural unit of (1-2) _b and (1-2) appears in the vicinity of −10 to −30 ppm, and (R ⁶ SiO _{3/2 of the} above general formula (1)). ) Each peak corresponding to the trifunctional structural units of _c , (1-3) and (1-4) appears in the vicinity of −50 to −70 ppm, and (SiO _4/2 ) _{d of} the above general formula (1), ( 1-5), tetrafunctional structure of (1-6) and (1-7) Each peak corresponding to the position appears in the vicinity of -90~-120ppm.
Therefore, it is possible to measure the ratio of the general formula (1) by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.
However, when the ²⁹ Si-NMR measurement based on the TMS cannot be distinguished from the functional structural unit of the general formula (1), not only the ²⁹ Si-NMR measurement result but also 1H-NMR or 19F The ratio of the structural units can be discriminated by using the results measured by -NMR as necessary.

The silicone resin preferably has a structural unit of R ⁷ R ⁸ SiO _2/2, a structural unit of R ⁹ SiO _3/2 and / or a structural unit of SiO _4/2 . By having a structural unit of R ⁷ R ⁸ SiO _2/2, a structural unit of R ⁹ SiO _3/2 and / or a structural unit of SiO _4/2 , the thermosetting composition for optical semiconductors of the present invention is Furthermore, it has the outstanding heat resistance, and can prevent problems, such as film loss under use conditions. In addition, it is preferable to appropriately include the SiO _4/2 structural unit because the viscosity of the thermosetting composition for optical semiconductors of the present invention can be easily adjusted to a desired range. The above silicone resin, if it contains only structural units of R ⁷ R ⁸ SiO _2/2, for an optical semiconductor thermosetting composition of the present invention, or a insufficient heat resistance and three-dimensional Crosslinking tends to be insufficient, and film loss may occur after curing.
At least one of the above R ^{7 to} R ⁹ is a cyclic ether-containing group, and R ^{7 to} R ⁹ other than the cyclic ether-containing group are linear, branched or cyclic hydrocarbons having 1 to 8 carbon atoms or It represents the fluorinated product, and these may be the same or different from each other. As such R < ⁷ > -R < ⁹ >, the thing similar to R < ⁴ > -R < ⁶ > mentioned above is mentioned, for example. Furthermore, the structural unit of R ⁷ R ⁸ SiO _2/2 , the structural unit of R ⁹ SiO _3/2 , and the structural unit of SiO _4/2 include the above general formulas (1-2) to (1-7 The same structure as the bifunctional structural unit, trifunctional structural unit and tetrafunctional structural unit represented by

In the thermosetting composition for optical semiconductors of the present invention, having a structural unit of R ⁷ R ⁸ SiO _2/2, a structural unit of R ⁹ SiO _3/2 and / or a structural unit of SiO _4/2 And a resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 and / or a structural unit of SiO _4/2 in a skeleton of one molecule in an uncured state A mixture of a resin having a structural unit of only R ⁷ R ⁸ SiO _2/2 and a resin having a structural unit of R ⁹ SiO _3/2 and / or a resin having a structural unit of SiO _4/2 may be used. May be. Of these, a resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule of the resin is preferable.

The resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule is represented by a = d = 0 in the general formula (1). Can be used.
In this case, the preferable lower limit of b / (a + b + c + d) is 0.5, the preferable upper limit is 0.95, the more preferable lower limit is 0.6, and the more preferable upper limit is 0.9 (hereinafter, condition (1)) Also called). The preferable lower limit of c / (a + b + c + d) is 0.05, the preferable upper limit is 0.5, the more preferable lower limit is 0.1, and the more preferable upper limit is 0.4 (hereinafter also referred to as condition (2)).

Specific examples of the resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule of the silicone resin include, for example, an average composition formula represented by the following general formula: The resin represented by (2), (3), (4) or (5) can be used.

In the general formula (2), R ¹² represents a cyclic ether-containing group, R ¹⁰ and R ¹¹ represent a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, These may be the same as each other or different. e / (e + f) satisfies the above condition (1), and f / (e + f) satisfies the above condition (2).

In the general formula (3), R ¹⁴ and / or R ¹⁵ is a cyclic ether-containing group, and R ¹³ is a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. To express. When only one of R ^{14 and} R ¹⁵ is a cyclic ether, the other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. g / (g + h) satisfies the above condition (1), and h / (g + h) satisfies the above condition (2).

In the general formula (4), R ¹⁸ and / or R ¹⁹ is a cyclic ether-containing group, and R ¹⁶ , R ¹⁷ , and R ²⁰ are linear, branched, or cyclic carbon atoms having 1 to 8 carbon atoms. It represents hydrogen or a fluorinated product thereof, and these may be the same as or different from each other. When only one of R ^{18 and} R ¹⁹ is a cyclic ether, the other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. (I + j) / (i + j + k) satisfies the above condition (1), and k / (i + j + k) satisfies the above condition (2).

In the general formula (5), R ²³ is a cyclic ether-containing group, and R ²¹ , R ²² , and R ²⁴ are linear, branched, or cyclic hydrocarbons having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. l / (l + m + n) satisfies the condition (1), and (m + n) / (l + m + n) satisfies the condition (2).

Especially, it is preferable to contain the resin component represented by the said General formula (2) or (5). In the general formulas (2) to (5), the cyclic ether-containing group preferably contains either one of a glycidyl group or an epoxycyclohexyl group.

The resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule is a cyclic ether-containing group in the structural unit of R ⁹ SiO _3/2. It is preferable to have. When the cyclic ether-containing group is contained in the structural unit of R ⁹ SiO _3/2 , the cyclic ether-containing group is likely to come out of the polysiloxane skeleton of the silicone resin, and the thermosetting composition for optical semiconductors of the present invention The cured product has a sufficient three-dimensional cross-linked structure to have sufficient heat resistance, and it can be suitably prevented that film loss occurs in the cured product.

A resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule, wherein the cyclic ether-containing group is contained in the structural unit of R ⁹ SiO _3/2 As the resin having, for example, the average composition formula is preferably represented by the following general formula (6), (7) or (8).

一般式（６）中、ｏ、ｐは、ｏ／（ｏ＋ｐ）＝０．６〜０．９５、ｐ／（ｏ＋ｐ）＝０．０５〜０．４を満たし、Ｒ^２７が環状エーテル含有基であり、Ｒ^２５、Ｒ^２６は、炭素数１〜８の炭化水素或いはフッ素化物であり、これらは互いに同一であってもよく、異なっていてもよい。

In the general formula (6), o and p satisfy o / (o + p) = 0.6 to 0.95, p / (o + p) = 0.05 to 0.4, and R ²⁷ is a cyclic ether-containing group. R ²⁵ and R ²⁶ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different.

一般式（７）中、ｑ、ｒ、ｓは、（ｑ＋ｒ）／（ｑ＋ｒ＋ｓ）＝０．６〜０．９５、ｓ／（ｑ＋ｒ＋ｓ）＝０．０５〜０．４を満たし、Ｒ^３２が環状エーテル含有基であり、Ｒ^２８〜Ｒ^３１は、炭素数１〜８の炭化水素或いはフッ素化物であり、これらは互いに同一であってもよく、異なっていてもよい。ただし、（Ｒ^２８Ｒ^２９ＳｉＯ_２／２）と（Ｒ^３０Ｒ^３１ＳｉＯ_２／２）とは構造が異なるものである。

In general formula (7), q, r, and s satisfy (q + r) / (q + r + s) = 0.6 to 0.95, s / (q + r + s) = 0.05 to 0.4, and R ³² is cyclic It is an ether-containing group, and R ^{28 to} R ³¹ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different. However, (R ²⁸ R ²⁹ SiO _2/2 ) and (R ³⁰ R ³¹ SiO _2/2 ) have different structures.

一般式（８）中、ｔ、ｕ、ｖは、ｔ／（ｔ＋ｕ＋ｖ）＝０．６〜０．９５を満たし、（ｕ＋ｖ）／（ｔ＋ｕ＋ｖ）＝０．０５〜０．４を満たし、Ｒ^３６が環状エーテル含有基であり、Ｒ^３３、Ｒ^３４、Ｒ^３５は、炭素数１〜８の炭化水素或いはフッ素化物であり、これらは互いに同一であってもよく、異なっていてもよい。

In general formula (8), t, u, and v satisfy t / (t + u + v) = 0.6 to 0.95, satisfy (u + v) / (t + u + v) = 0.05 to 0.4, and R ³⁶ Is a cyclic ether-containing group, and R ³³ , R ³⁴ , and R ³⁵ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different.

In the thermosetting composition for optical semiconductors of the present invention, the silicone resin preferably has a cyclic ether-containing group and a polysiloxane skeleton bonded via a silicon-carbon bond. Since the cyclic ether-containing group and the polysiloxane skeleton are bonded via a silicon-carbon bond, the thermosetting composition for an optical semiconductor of the present invention is excellent in heat resistance, light resistance, and film reduction. This is preferable. For example, when a resin obtained by an addition reaction in which an OH group is reacted is used, a cyclic ether-containing group and a polysiloxane skeleton are bonded via a silicon-oxygen bond. In addition to the fact that sufficient light resistance and light resistance may not be obtained, film loss may be deteriorated.

The silicone resin preferably contains an alkoxy group with a lower limit of 0.5 mol% and an upper limit of 10 mol%. By containing such an alkoxy group, heat resistance and light resistance are drastically improved. This is presumably because the curing rate can be drastically improved by containing an alkoxy group in the silicone resin, thereby preventing thermal degradation during curing.

Further, since the curing speed is dramatically improved as described above, sufficient curability can be obtained even when the amount of the curing accelerator added is relatively small.

If the alkoxy group is less than 0.5 mol%, the curing rate may not be sufficiently obtained and the heat resistance may be deteriorated. If it exceeds 10 mol%, the storage stability of the silicone resin or the composition may be deteriorated. , Heat resistance may deteriorate. A more preferred lower limit is 1 mol%, and a more preferred upper limit is 5 mol%.

In the present specification, the content of the alkoxy group means the amount of the alkoxy group contained in the average composition of the silicone resin component.

The silicone resin preferably does not contain a silanol group. The silanol group is not preferable because the storage stability of the polymer is remarkably deteriorated and the storage stability when the resin composition is obtained is also remarkably deteriorated. Such silanol groups can be reduced by heating under vacuum, and the amount of silanol groups can be measured using infrared spectroscopy or the like.

In the thermosetting composition for optical semiconductors of the present invention, the preferable lower limit of the number average molecular weight (Mn) of the silicone resin is 1000, and the preferable upper limit is 50,000. If it is less than 1000, volatile components increase at the time of thermosetting, and film loss increases when used as a sealant, which is not preferable. If it exceeds 50,000, viscosity adjustment becomes difficult, which is not preferable. A more preferred lower limit is 1500, 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 method for synthesizing the silicone resin is not particularly limited, and examples thereof include (1) a method (method (1)) in which a siloxane compound and a siloxane compound having a cyclic ether-containing group are subjected to a condensation reaction.

In the method (1), examples of the siloxane compound include alkoxysilanes having a siloxane unit represented by the following general formulas (9), (10), (11), and (12), or partial hydrolysates thereof.

In the general formulas (9) to (12), R ^{37 to} R ⁴² represent a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or A branched alkoxy group having 1 to 4 carbon atoms is represented.

In the general formulas (9) to (12), when R ^{37 to} R ⁴² are linear, branched or cyclic hydrocarbons having 1 to 8 carbon atoms, specifically, for example, methyl group, ethyl Group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group , Neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, phenyl group and the like.

In the general formulas (9) to (12), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, an ethoxy group, n -Propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

In the siloxane compound, the compounding ratio of the alkoxysilane having a siloxane unit represented by the general formulas (9) to (12) or a partial hydrolyzate thereof is subjected to a condensation reaction with a siloxane compound having a cyclic ether-containing group described later. The silicone resin synthesized in this manner is appropriately adjusted so as to have a structure represented by the above general formula (1), preferably a structure represented by any one of the above general formulas (2) to (8).

Examples of the siloxane compound having a cyclic ether-containing group include alkoxysilanes having a cyclic ether-containing group represented by the following general formulas (13) and (14) or partial hydrolysates thereof.

In the general formulas (13) and (14), R ⁴³ and / or R ⁴⁴ and R ⁴⁵ are cyclic ether-containing groups, and only one of R ^{43 and} R ⁴⁴ is a cyclic ether-containing group. The other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In general formulas (13) and (14), R ⁴³ and / or R ⁴⁴ and the cyclic ether-containing group represented by R ⁴⁵ are not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Is mentioned. 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.

The epoxycyclohexyl group is not particularly limited, and examples thereof include 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, and the like.

In the general formula (13), when any one of R ⁴³ and / or R ⁴⁴ is a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, specifically, For example, the thing similar to what was demonstrated in the said General formula (1) is mentioned.

In the general formulas (13) and (14), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically the general formula (1-2) described above. The thing similar to what was demonstrated in-(1-7) is mentioned.

Specific examples of the siloxane compound having a cyclic ether-containing group represented by the general formula (13) include 3-glycidoxypropyl (methyl) dimethoxysilane and 3-glycidoxypropyl (methyl) di Ethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyl (methyl) diethoxysilane and the like.

Specific examples of the siloxane compound having a cyclic ether-containing group represented by the general formula (14) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2, Examples include 3-epoxypropyltriethoxysilane.

In the method (1), as a specific method for the condensation reaction of the siloxane compound and the siloxane compound having a cyclic ether-containing group, for example, the siloxane compound and the compound having a cyclic ether group are mixed with water and an acid. Or the method of making it react in presence of a basic catalyst and synthesize | combining a silicone resin is mentioned.
The siloxane compound may be reacted in advance in the presence of water and an acid or basic catalyst, and then the siloxane compound having a cyclic ether group may be reacted.

In the method (1), when the siloxane compound and the compound having a cyclic ether-containing group are reacted in the presence of water and an acid or a basic catalyst, the compound having the cyclic ether-containing group is It mix | blends so that a lower limit may be 0.1 mol% and an upper limit may be 50 mol% with respect to all the organic groups couple | bonded with the silicon atom of the said siloxane compound and the compound which has a cyclic ether containing group.

The blending amount of the water is not particularly limited as long as it is an amount capable of hydrolyzing the alkoxy group bonded to the silicon atom in the siloxane compound having the cyclic ether-containing group, and is appropriately adjusted.

The acidic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group. For example, inorganic acids such as phosphoric acid, boric acid, and carbonic acid; formic acid, acetic acid, propionic acid, and lactic acid , Lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, oleic acid and other organic acids; their acid anhydrides or derivatives .

The basic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group, and examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide; Examples include alkali metal alkoxides such as sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide; and alkali metal silanol compounds such as sodium silanolate compounds, potassium silanolate compounds, and cesium silanolate compounds. Of these, potassium-based catalysts and cesium-based catalysts are preferred.

The addition amount of the acid or basic catalyst is not particularly limited, but the preferred lower limit is 10 ppm and the preferred upper limit is 10,000 ppm with respect to the total amount of the siloxane compound and the siloxane compound having a cyclic ether-containing group, A more preferred lower limit is 100 ppm, and a more preferred upper limit is 5000 ppm.
The acid or basic catalyst may be added as it is, or may be added after dissolving in a small amount of water or the siloxane compound.

In the condensation reaction between the siloxane compound and the siloxane compound having a cyclic ether-containing group, the silicone resin to be synthesized can be prevented from precipitating from the reaction system, and the water and free water due to the condensation reaction can be removed azeotropically. Therefore, 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.

From the viewpoint of adjusting the amount of alkoxy groups, it is preferable to synthesize a silicone resin by the above method (1).
In order to bring the alkoxy group into an appropriate range, the above method (1) can bring the alkoxy group into an appropriate range by adjusting the reaction temperature, reaction time, amount of catalyst and amount of water. is there.

The thermosetting composition for optical semiconductors of the present invention preferably contains a bifunctional silicone resin having one or more glycidyl-containing groups in the molecule.
By containing such a bifunctional silicone resin, the thermosetting composition for optical semiconductors of the present invention significantly improves the crack resistance of the cured product. This is because the bifunctional silicone resin has a flexible skeleton compared to the silicone resin in the gap between the crosslinking points generated by the reaction of the cyclic ether-containing group of the silicone resin having a cyclic ether-containing group in the molecule in the cured product. It is guessed that this is because

In the present specification, the glycidyl-containing group only needs to contain a glycidyl group as at least a part of the group, and may contain, for example, another skeleton such as an alkyl group or an alkyl ether group and a glycidyl group. Means group.
The glycidyl-containing group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy A propyl group, 4-glycidoxybutyl group, etc. are mentioned.

As the bifunctional silicone resin, for example, a resin represented by a = c = d = 0 in the general formula (1) can be used. Specifically, the average composition formula is represented by the following general formula (15 It is preferable to contain the resin component represented by (16) or (16). When the bifunctional silicone resin contains the resin component represented by the following general formula (15) or (16), the cured product of the thermosetting composition for optical semiconductors of the present invention has appropriate flexibility. Therefore, the crack resistance is extremely excellent. The bifunctional silicone resin has an average composition formula represented by the following general formula (15) or (16). The thermosetting composition for optical semiconductors of the present invention is represented by the following general formula. When it is a mixture containing not only the resin component represented by (15) or (16) but also a resin component having various structures, the following generality is obtained by taking the average of the composition of the resin component contained: This also means the case represented by formula (15) or (16).

一般式（１５）中、Ｒ^４８及び／又はＲ^４９は、グリシジル含有基であり、Ｒ^４６、Ｒ^４７は、直鎖状、分岐状若しくは環状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。また、Ｒ^４８又はＲ^４９のいずれか一方のみがグリシジル含有基である場合、他方は、直鎖状、分岐状若しくは環状の炭素数１〜８の炭化水素或いはそのフッ素化物を表す。また、ｗ／（ｗ＋ｘ）の好ましい下限は０．６、好ましい上限は０．９５、より好ましい下限は０．７、より好ましい上限は０．９であり、ｘ／（ｗ＋ｘ）の好ましい下限は０．０５、好ましい上限は０．４、より好ましい下限は０．１、より好ましい上限は０．３である。

In the general formula (15), R ⁴⁸ and / or R ⁴⁹ is a glycidyl-containing group, and R ⁴⁶ and R ⁴⁷ are linear, branched or cyclic hydrocarbons having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. When only one of R ^{48 and} R ⁴⁹ is a glycidyl-containing group, the other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit for w / (w + x) is 0.6, the preferred upper limit is 0.95, the more preferred lower limit is 0.7, the more preferred upper limit is 0.9, and the preferred lower limit for x / (w + x) is 0. 0.05, a preferred upper limit is 0.4, a more preferred lower limit is 0.1, and a more preferred upper limit is 0.3.

一般式（１６）中、Ｒ^５４及び／又はＲ^５５は、グリシジル含有基であり、Ｒ^５０、Ｒ^５１、Ｒ^５２、Ｒ^５３は、直鎖状、分岐状若しくは環状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。また、Ｒ^５４又はＲ^５５のいずれか一方のみがグリシジル含有基である場合、他方は、直鎖状、分岐状若しくは環状の炭素数１〜８の炭化水素或いはそのフッ素化物を表す。また、ｙ＋ｚ／（ｙ＋ｚ＋Ａ）の好ましい下限は０．６、好ましい上限は０．９５、より好ましい下限は０．７、より好ましい上限は０．９であり、Ａ／（ｙ＋ｚ＋Ａ）の好ましい下限は０．０５、好ましい上限は０．４、より好ましい下限は０．１、より好ましい上限は０．３である。

In the general formula (16), R ⁵⁴ and / or R ⁵⁵ is a glycidyl-containing group, and R ⁵⁰ , R ⁵¹ , R ⁵² , and R ⁵³ are linear, branched, or cyclic having 1 to 8 carbon atoms. It represents a hydrocarbon or a fluorinated product thereof, and these may be the same as or different from each other. When only one of R ^{54 and} R ⁵⁵ is a glycidyl-containing group, the other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit of y + z / (y + z + A) is 0.6, the preferred upper limit is 0.95, the more preferred lower limit is 0.7, the more preferred upper limit is 0.9, and the preferred lower limit of A / (y + z + A) is 0. 0.05, a preferred upper limit is 0.4, a more preferred lower limit is 0.1, and a more preferred upper limit is 0.3.

The preferable lower limit of the number average molecular weight (Mn) of the bifunctional silicone resin is 1500, and the preferable upper limit is 50,000. When it is less than 1500, the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention may be insufficient, and when it exceeds 50,000, the thermosetting composition for optical semiconductors of the present invention. It may be difficult to adjust the viscosity. A more preferable lower limit is 2000, and a more preferable upper limit is 20,000.

The method for synthesizing such a bifunctional silicone resin is not particularly limited, and examples thereof include a method (method (2)) in which an alkoxysilane compound and an alkoxysilane compound having a glycidyl-containing group are subjected to a condensation reaction.

When the bifunctional silicone resin is synthesized by the method (2), the alkoxysilane compound is not particularly limited, and examples thereof include the same compounds as the dialkoxysilane compound of the general formula (10) described above.
Moreover, as an alkoxysilane compound which has the said glycidyl containing group, the thing similar to the dialkoxysilane compound of General formula (13) mentioned above is mentioned, for example.

Specific examples of the dialkoxysilane having a glycidyl-containing group include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl ( And methyl) dibutoxysilane and 2,3-epoxypropyl (methyl) dimethoxysilane.

Specific examples of the condensation reaction of the alkoxysilane compound and the alkoxysilane compound having a glycidyl-containing group include, for example, an alkoxysilane compound having a cyclic ether-containing group and an alkoxysilane compound in the case of synthesizing the above-described silicone resin. The same method as that in the case of reacting is mentioned.

In the thermosetting composition for optical semiconductors of the present invention, the blending amount of the bifunctional silicone resin with respect to the silicone resin described above is not particularly limited, but the preferred lower limit is 10 parts by weight with respect to 100 parts by weight of the silicone resin. A preferred upper limit is 120 parts by weight. When the amount is less than 10 parts by weight, the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention may not be sufficiently exhibited, and when it exceeds 120 parts by weight, the thermosetting for optical semiconductors of the present invention is performed. The cured product of the curable composition is inferior in heat resistance, and the cured product may be easily yellowed in a thermal environment. A more preferred lower limit is 15 parts by weight, and a more preferred upper limit is 100 parts by weight.

The curable composition for optical semiconductor elements of this invention contains the compound which has at least 1 radically polymerizable unsaturated group and at least 1 silane group in a molecule | numerator.
Since the radical polymerizable compound has a radical polymerizable unsaturated group, in the curable composition for optical semiconductor elements of the present invention, the radical polymerizable compound reacts to form a polymer. Since the radical polymerizable compound has a silane group, it is highly compatible with the silicone resin, and forms a polymer in a finely dispersed state in the curable composition for optical semiconductor elements of the present invention. To do. At this time, on the one hand, the curing of the silicone resin proceeds, but the polymerization reaction rate at which the radical polymerizable compound forms a polymer is much faster than the curing reaction rate at which the silicone resin is cured. In the obtained cured product, the polymer of the radical polymerizable compound is surely formed. Therefore, also in the obtained cured product, the polymer of the radical polymerizable compound exists in a uniformly dispersed state. As a result, since the polymer of the radical polymerizable compound functions as a stress relaxation agent, it can prevent the occurrence of cracks, peeling, etc. even when a sudden thermal change is caused by a thermal cycle, and can be used for a long time. It is possible to increase the durability. Further, in the obtained cured product, the polymer of the radical polymerizable compound exists in a uniformly dispersed state, so that the transparency and the like exhibited by the silicone resin are not hindered.

The silane group is not particularly limited, but preferably has a siloxane bond in which silicon and oxygen are alternately bonded. When the radical polymerizable compound has a siloxane bond, the compatibility with the silicone resin is further increased, and the curable composition for optical semiconductor elements of the present invention can exhibit excellent dispersibility.

The radical polymerizable compound is preferably a monomer or an oligomer. When the radical polymerizable compound is a polymer, the compatibility with the silicone resin may deteriorate.

The radically polymerizable unsaturated group is not particularly limited, and examples thereof include an allyl group, a vinyl group, and a (meth) acryl group. Of these, a (meth) acryl group is preferred because of its high reactivity.

The radical polymerizable compound having the (meth) acryl group is not particularly limited as long as it has the silane group, and CH ₂ = CHCOOCH ₂ CH _2- , (CH ₂ = C (CH ₃ ) COOCH ₂ ). _{3 C-CH 2 -, (} CH 2 = CHCOOCH 2) 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 2 C (C 2 H 5) CH 2 -, CH 2 = C (CH 3) COOCH 2 _{CH 2 -, (CH 2 =} C (CH 3) COOCH 2) 2 C (C 2 H 5) -CH 2 -, (CH 2 = CHCOOCH 2) (CH 2 = C (CH 3) COOCH 2) CH- _{, CH 2 = CHCOOCH 2 CH (} CH 2 OC 6 H 5) -, CH 2 = CHCOOCH 2 -Si (CH 3) 2 -, _and, CH ₂ = CHCOOCH 2 CH 2 _{H 2 -Si (CH 3) 2} - 1~3 one acryloyloxy group or methacryloyloxy 1 to 10 carbon atoms which is substituted by a group, preferably C2-6 alkyl groups such as, aryloxy-substituted alkyl group, Although silane compound having an alkyl group connected like a diorgano silyl group, _{preferably, CH 2 = CHCOOCH 2 CH 2} -, (CH 2 = C (CH 3) COOCH 2) 3 C-CH 2 -, _{(CH 2 = CHCOOCH 2) 3} C-CH 2 -, (CH 2 = CHCOOCH 2) 2 C (C 2 H 5) CH 2 -, CH 2 = C (CH 3) COOCH 2 CH 2 -, (CH 2 _{= C (CH 3) COOCH 2} ) 2 C (C 2 H 5) -CH 2 -, (CH 2 = CHCOOCH 2) (CH 2 = C (CH 3) COOCH 2) C _{-, CH 2 = CHCOOCH 2 CH} (CH 2 OC 6 H 5) - silane compound having a group, and the like.
Specifically, for example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropyl Methyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutyl Phenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyl Phenylmethyl Toxisilane, γ- (meth) acryloxypropylphenylmethylethoxysilane, γ- (meth) acryloxypropyltrisilanol, γ- (meth) acryloxypropylmethyldihydroxysilane, γ- (meth) acryloxybutylphenyldihydroxysilane, and monomers such as γ- (meth) acryloxypropyldimethylhydroxysilane, γ- (meth) acryloxypropylphenylmethylhydroxysilane, and the like.

There are no particular restrictions regarding the oligomer, _{e.g., CH 2 = CHCOOCH 2 CH 2} -, (CH 2 = C (CH 3) COOCH 2) 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 3 C-CH _{2 -, (CH 2 = CHCOOCH} 2) 2 C (C 2 H 5) CH 2 -, CH 2 = C (CH 3) COOCH 2 CH 2 -, (CH 2 = C (CH 3) COOCH 2) 2 C _{(C 2 H 5) -CH 2} -, (CH 2 = CHCOOCH 2) (CH 2 = C (CH 3) COOCH 2) CH-, CH 2 = CHCOOCH 2 CH (CH 2 OC 6 H 5) -, CH _{2 = CHCOOCH 2 -Si (CH 3} ) 2 -, _{and, CH 2 = CHCOOCH 2 CH 2} CH 2 -Si (CH 3) 2 - 1~3 one acryloyloxy groups such as Is a silane compound having an alkyl group substituted with a methacryloyloxy group having 1 to 10, preferably 2 to 6 carbon atoms, preferably an aryloxy-substituted alkyl group, a diorganosilyl group, and the like, _{preferably, CH 2 = CHCOOCH 2 CH 2} -, (CH 2 = C (CH 3) COOCH 2) 3 C-CH 2 -, (CH 2 = CHCOOCH 2) 3 C-CH 2 -, (CH 2 = CHCOOCH _{2) 2 C (C 2 H} 5) CH 2 -, CH 2 = C (CH 3) COOCH 2 CH 2 -, (CH 2 = C (CH 3) COOCH 2) 2 C (C 2 H 5) -CH _{2 -, (CH 2 = CHCOOCH} 2) (CH 2 = C (CH 3) COOCH 2) CH-, CH 2 = CHCOOCH 2 CH (CH 2 OC 6 H 5) - Examples thereof include silane compounds having a group or the like.

It is not specifically limited as a commercial item of the above-mentioned radical polymerization compound, for example, FM7711, FM7721, FM0711, FM0721, TM0701, TM0701T (all are the Chisso company make), BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 (all of which are manufactured by Big Chemie Japan) and the like.

The radical polymerizable compound preferably has a molecular weight of 5000 or less. When the molecular weight exceeds 5000, the compatibility with the silicone resin may be deteriorated. The molecular weight is more preferably 2000 or less, still more preferably 1000 or less, and particularly preferably 500 or less.

The blending amount of the radical polymerizable compound is not particularly limited, but a preferable lower limit is 0.1 part by weight and a preferable upper limit is 20 parts by weight with respect to 100 parts by weight of the silicone resin having a cyclic ether group. If the amount is less than 0.1 part by weight, the function of stress relaxation by the obtained polymer may not be sufficiently exhibited. When it exceeds 20 parts by weight, the compatibility between the silicone resin and the radical polymerizable compound may be deteriorated. A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 10 parts by weight.

The curable composition for optical semiconductor elements of the present invention contains a curing agent that reacts with the cyclic ether-containing group.
The curing agent plays a role of curing the silicone resin.

It does not specifically limit as said hardening | curing agent, For example, a thermosetting agent, a photocuring agent, etc. are mentioned.
The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group, and examples thereof include ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylamino. Aliphatic amines such as piperazine and isophoronediamine, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenormethane, 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, brominated bisphenol A Phenolic resins such as novolac; polyols obtained by hydrogenating aromatic rings of these phenolic resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydroanhydride Taric acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic Acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride Such as alicyclic acid anhydrides, such as 3-methylglutaric anhydride, 3-alkylglutaric anhydride having an optionally branched alkyl group having 1 to 8 carbon atoms, 2-ethyl-3-propyl 2,3-dialkylglutaric anhydride having an optionally branched alkyl group having 1 to 8 carbon atoms, such as glutaric anhydride, 2,4-diethylglutaric anhydride Alkyl-substituted glutaric anhydrides such as 2,4-dialkylglutaric anhydrides having an optionally branched alkyl group having 1 to 8 carbon atoms such as 2,4-dimethylglutaric anhydride, phthalic anhydride , Aromatic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and salts thereof, and the above aliphatic amines Amine amines obtained by reaction of aromatic amines and / or imidazoles with epoxy resins, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene Tertiary amines such as 7; organic phosphines such as triphenylphosphine; and dicyandiamide. It is. These thermosetting agents may be used independently and 2 or more types may be used together.

Among these, acid anhydrides such as alicyclic acid anhydrides, alkyl-substituted glutaric acid anhydrides, and aromatic acid anhydrides are preferable, and alicyclic acid anhydrides and alkyl-substituted glutaric acid anhydrides are more preferable. And particularly preferably methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, cyclohexane-1,2. , 3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, 2,4-diethylglutaric anhydride.
In particular, since the transparency of the curable composition for optical semiconductor elements of the present invention is high, an acid anhydride is preferable.

The photocuring agent is not particularly limited as long as it can react with the cyclic ether-containing group. For example, an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a sulfonimide compound, a diazosulfone compound, Examples include disulfonylmethane compounds, nitrobenzyl compounds, naphthoquinonediazide compounds, and the like.

The onium salt compound is not particularly limited, and examples thereof include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like. Specific examples include bis (4-tert-butylphenyl). Iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium-2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium -10-camphorsulfonate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium Fluorobutanesulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-10-camphorsulfonate, diphenyliodonium-p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium- 2-trifluoromethylbenzenesulfonate, triphenylsulfonium-10-camphorsulfonate, triphenylsulfonium-p-toluenesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium nonafluorobutanesulfonate , 4-ter -Butylphenyldiphenylsulfonium-2-trifluoromethylbenzenesulfonate, 4-tert-butylphenyldiphenylsulfonium-10-camphorsulfonate, 4-tert-butylphenyldiphenylsulfonium-p-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium Trifluoromethanesulfonate, 4-tert-butoxyphenyldiphenylsulfonium nonafluorobutanesulfonate, 4-tert-butoxyphenyldiphenylsulfonium-2-trifluoromethylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium-10-camphorsulfonate, 4- tert-Butoxyphenyldiphenylsulfonium-p-toluenesulfo And the like.

The sulfone compound is not particularly limited, and examples thereof include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples include phenacylphenylsulfone, mesitylphenacylsulfone, bis (Phenylsulfonyl) methane, 4-tris (phenacyl) sulfone and the like can be mentioned.

The sulfonic acid ester compound is not particularly limited, and examples thereof include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like, and specific examples include benzoin tosylate, pyrogallol tris (tri Fluorosulfonate), pyrogallol methanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α-methylolbenzoin octanesulfonate, α-methylolbenzoin trifluoromethanesulfonate, α-methylolbenzoindodecylsulfonate, etc. It is done.

The sulfonimide compound is not particularly limited. For example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-dioxy-2,3-dicarboximide, N- (tri Fluoromethylsulfonyloxy) naphthylimide, N- (camphorsulfonylthio) Succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) dicyclo [2.2.1] hept-5-ene-2,3-dicarboxy N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-dioxy-2,3-dicarboximide, N- (camphorsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenyl monomer Imido, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-dioxy-2,3- Dicarboximide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2- Trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfuride) Phonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-dioxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- ( 4-fluorophenylsulfonyloxy) naphthylimide and the like.

Although it does not specifically limit as a compounding quantity of the said hardening | curing agent, A preferable minimum is 1 weight part with respect to 100 weight part of said silicone resins, and a preferable upper limit is 200 weight part. Within this range, the encapsulant for optical semiconductors 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.

The curable composition for optical semiconductor elements of this invention contains the polymerization initiator which reacts with the said radically polymerizable unsaturated group.
The polymerization initiator plays a role of polymerizing the radical polymerizable compound.

The polymerization initiator is not particularly limited, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator.
The thermal radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, and 2,2′-azobis-2. , 4-dimethylvaleronitrile, 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovaleric acid, 2,2 ′ -Azobis (2-amidinopropene) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2,2'-azobis (2-methylpropionamide) dihydrate, 2,2'-azobis (2, Azo compounds such as 4,4-trimethylpentane), tert-butylperoxyneodecanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexyl Noate, tert-butyl peroxyisobutyrate, tert-butyl peroxylaurate, tert-butyl peroxyisophthalate, tert-butyl peroxyacetate, tert-butyl peroxyoctoate, tert-butyl peroxybenzoate, etc. Peroxyesters, diacyl peroxides such as benzoyl peroxide, hydroperoxides such as cumene hydroperoxide, methyl ethyl ketone peroxide, potassium persulfate, 1,1-bis (tert-butylperoxy) -3, Examples include 3,5-trimethylcyclohexane, dialkyl peroxides or peroxydicarbonates, hydrogen peroxide, and the like.

The radical photopolymerization initiator is not particularly limited, and examples thereof include benzoins such as benzoin and benzoin methyl ether, benzophenones such as benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, and 4,4′-bisdiethylaminobenzophenone. , Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, N, N-dimethylaminoacetophenone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholinopropan-1-one, 2-methylanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthracone Anthraquinones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthones such as 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Examples include ketals.

The polymerization initiator is preferably a borate compound.
The borate compound can be suitably used because it can react with both the cyclic ether group and the radical polymerizable unsaturated group.
In this specification, the borate compound refers to a compound having a structure represented by [Br ¹ r ² r ³ r ⁴ ] ⁻ , and B represents a boron atom.

In the borate compound, r ^{1 to} r ⁴ are a fluoro group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, and an optionally substituted allyl group. Represents an alicyclic group which may be substituted, and these may be the same or different from each other.

As the alkyl group which may be substituted, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 3-methoxypropyl group, 4-chlorobutyl group, 2-diethylaminoethyl group and the like.

The alkenyl group which may be substituted is preferably a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, for example, a vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group. , Dodecynyl group, prenyl group and the like.

Examples of the allyl group which may be substituted include, for example, phenyl group, tolyl group, xylyl group, 4-ethylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-methoxyphenyl group, 4 -A diethylaminophenyl group, 2-methylphenyl group, 2-methoxyphenyl group, naphthyl group, 4-methylnaphthyl group, etc. are mentioned.

Examples of the optionally substituted aralkyl group include a benzyl group, a phenethyl group, a propiophenyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, and a p-methoxybenzyl group.

Examples of the alicyclic group which may be substituted include a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group, and a cycloheptyl group.

The borate compound is not particularly limited, and for example, tetrafluoroborate, tetraphenylborate, tetraethylborate, tetrabutylborate, tetrakis (4-methylphenyl) borate, tetrakis (4-tert-butylphenyl) borate, tetrakis (4 -Fluorophenyl) borate, tetrakis (4-methoxyphenyl) borate, tetrakis (2,3,4,5,6-pentafluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, butyl Examples thereof include compounds having trisphenyl borate, butyl tris-4-tert-butyl phenyl borate, butyl trisnaphthyl borate and the like in the molecule.

In particular, in the borate compound, three of r ^{1 to} r ⁴ are the above-described optionally substituted aryl groups, and one is the above-described optionally substituted alkyl group, the alkyl group is It is preferable because it is considered that it traps radical species that are eliminated as radicals and cause yellowing substance generation.
Such a borate compound is not particularly limited, and examples thereof include butyl trisphenyl borate, butyl tris-4-tert-butylphenyl borate, and butyl trisnaphthyl borate.
Specifically, tetra-n-butylammonium cation butyltrisphenylborate, tetra-n-butylammonium cation butyltris-4-tert-butylphenylborate, tetra-n-butylammonium cation butyltrisnaphthylborate, tetraphenylammonium Cationic butyl trisphenyl borate, tetraphenyl ammonium cation butyl tris-4-tert-butyl phenyl borate, tetraphenyl ammonium cation butyl trisnaphthyl borate, tetra-n-butyl phosphonium cation butyl trisphenyl borate, tetra-n-butyl phosphonium cation butyl Tris-4-tert-butylphenylborate, tetra-n-butylphosphonium cation butyltrisnaphthy Borate, tetraphenylphosphonium cation butyl tris tetraphenylborate, tetraphenylphosphonium cation butyl tris -4-tert-butylphenyl borate, tetraphenylphosphonium cation-butyl tri snuff chill borate and the like.

The blending amount of the polymerization initiator is not particularly limited, but a preferable lower limit is 0.01 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total amount of the silicone resin and the radical polymerizable compound. . If it is less than 0.01 part by weight, the polymerization may not be carried out sufficiently. If it exceeds 10 parts by weight, it may be easily colored by heat, light, or the like. A more preferred lower limit is 0.1 parts by weight, and a more preferred upper limit is 5 parts by weight.

When the curable composition for optical semiconductor elements of the present invention contains a thermosetting agent as the curing agent, it preferably contains a thermal radical polymerization initiator as the polymerization initiator, and photocuring as the curing agent. When it contains an agent, it is preferable to contain a radical photopolymerization initiator as the polymerization initiator.
Thus, when containing a heat | fever or photocuring agent and a heat | fever or photoradical polymerization initiator, while giving the heat | fever or light, while hardening the said silicone resin, the said radically polymerizable compound can be polymerized. That is, since the radical polymerizable compound has a silicone skeleton, it is finely dispersed in the curable composition for optical semiconductor elements of the present invention. The radically polymerizable compound forms a polymer. Here, the polymerization reaction rate at which the radical polymerizable compound forms a polymer is much faster than the curing reaction rate at which the silicone resin is cured. Therefore, the polymer of the radical polymerizable compound is surely formed, and the polymer of the radical polymerizable compound is uniformly dispersed in the obtained cured product. As a result, the obtained cured product has excellent transparency and the like, and can exhibit excellent crack resistance. Further, in the obtained cured product, the polymer of the predetermined compound is present in a uniformly dispersed state, and thus does not hinder the high transparency that is derived from the predetermined silicone resin.

In addition, when the curable composition for optical semiconductor elements of the present invention contains a thermosetting agent as the curing agent, it may contain a radical photopolymerization initiator as the polymerization initiator, or as the curing agent. When a photocuring agent is contained, a thermal radical polymerization initiator may be contained as the polymerization initiator.
Even in such a case, as the curing of the silicone resin proceeds, the radical polymerizable compound only needs to form a polymer, and the silicone resin is cured by appropriately adjusting the applied heat or light. It is preferable to polymerize the radical polymerizable compound earlier. Even if an attempt is made to polymerize the radical polymerizable compound after the silicone resin is cured, the polymer of the radical polymerizable compound is not sufficiently formed in the resulting cured product, and the desired crack resistance cannot be obtained. Sometimes.

The curable composition for optical semiconductor elements of the present invention preferably further contains an antioxidant.
As the antioxidant, for example, a sulfur-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, a phenol-based antioxidant, and the like are preferable.

The curable composition for optical semiconductor elements of the present invention may further contain silica fine powder, high molecular weight silicone resin, or the like in order to adjust the viscosity.

Although it does not specifically limit as a viscosity of the curable composition 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 may occur when used as a sealing agent for an optical semiconductor element, and the optical semiconductor element may not be sealed. The semiconductor element may not be 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 cured product of the curable composition 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 curable composition for optical semiconductor elements 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 curable composition for optical semiconductor elements of this invention, and the transmittance | permeability of the light of wavelength 400nm made from Hitachi, Ltd. "U-4000. It is the value measured using "."
Moreover, it is preferable that the hardened | cured material of the curable composition 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 curable composition for optical semiconductor elements of the present invention will be insufficient. The light resistance test described above is a 1 mm thick cured product obtained by curing the curable composition 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 examination of irradiating / cm ² at 24 hours, the light transmittance after light resistance test using the above cured product after the light resistance test, manufactured by Hitachi, Ltd. and the transmittance of light having a wavelength of 400nm "U- It is a value measured using "4000".
Moreover, it is preferable that the hardened | cured material of the curable composition 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 curable composition for optical semiconductor elements of the present invention will be insufficient. The heat resistance test is a test in which a cured product having a thickness of 1 mm obtained by curing the curable composition for optical semiconductor elements of the present invention is left in an oven at 150 ° C. for 1500 hours. The light 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 method for producing the curable composition for optical semiconductor elements of the present invention is not particularly limited, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three roll, a bead mill, Examples include a method of mixing each predetermined amount of a silicone resin, a radical polymerizable compound, the curing agent, the polymerization initiator, and, if necessary, an antioxidant at room temperature or under heating.

Although it does not specifically limit as a use of the curable composition for optical semiconductor elements of this invention, For example, die-bonding materials for connecting to a sealing agent, a housing material, a lead electrode, a heat sink, etc., optical semiconductor elements, such as a light emitting diode When the light emitting element is flip-chip mounted, it can be used as an underfill material or a passivation film on the light emitting element. Especially, since the optical semiconductor device which can take out the light by the light emission from an optical semiconductor element efficiently can be manufactured, it can use suitably as a sealing agent, an underfill material, and a die-bonding material.

An optical semiconductor element can be manufactured by sealing a light emitting element using the curable composition for optical semiconductor elements of this invention. An optical semiconductor element using the curable composition for optical semiconductor elements of the present invention is also one aspect of the present 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.

When sealing the light emitting element using the curable composition for optical semiconductor elements of the present invention, other sealing agents may be used in combination as long as the effects of the present invention are not impaired. In this case, after sealing the light emitting element with the curable composition for optical semiconductor elements of the present invention, the periphery thereof may be sealed with the other sealing agent, and the light emitting element may be sealed with the other sealing element. After sealing with an agent, the periphery thereof may be sealed with the curable composition for optical semiconductor elements 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. Moreover, when a surface modifier is contained, a liquid can be applied to provide a protective layer on the surface.

The method for sealing the light emitting element with the curable composition for optical semiconductor elements of the present invention is not particularly limited. For example, the curable composition for optical semiconductor elements of the present invention is injected into a mold frame in advance, Examples include a method in which a lead frame having a light emitting element fixed thereon is immersed and cured, and a method in which the curable composition for an optical semiconductor element of the present invention is injected into a mold having the light emitting element inserted therein and cured.
Examples of the method for injecting the curable composition for optical semiconductor elements of the present invention include injection by a dispenser, transfer molding, injection molding and the like. Further, as other sealing methods, the curable composition for optical semiconductor elements of the present invention is dropped onto a light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, and the light emitting element at the bottom. The method etc. which inject | pour the curable composition for optical semiconductor elements of this invention with a dispenser etc. to the cup etc. which have arrange | positioned and harden | cure.
In any of the above methods, since the curable composition for optical semiconductor elements of the present invention has a viscosity in the above range, the curable composition for optical semiconductor elements of the present invention in which the light emitting element is sealed. Can be controlled very stably.

The method for curing the curable composition for optical semiconductor elements of the present invention is not particularly limited, and examples thereof include a heating method and a light irradiation method according to the type of the curing agent and polymerization initiator used. Can be mentioned. Here, as the curing of the silicone resin proceeds, the radical polymerizable compound may form a polymer, but the radical polymerizable compound is polymerized before the silicone resin is cured. Is preferred. Even if an attempt is made to polymerize the radical polymerizable compound after the silicone resin is cured, the polymer of the radical polymerizable compound is not sufficiently formed in the resulting cured product, and the desired crack resistance cannot be obtained. Sometimes.

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, light that is excellent in transparency, heat resistance, light resistance, and adhesion to a housing material, and can obtain a cured product that does not generate cracks or peeling even when subjected to a rapid thermal change due to a thermal cycle. It is possible to provide an encapsulant for a semiconductor element and an optical semiconductor element using the same.

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)
Dimethyldimethoxysilane (750 g) and 3-glycidoxypropylmethyldimethoxysilane (150 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was 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, and 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 = 11000 and Mw = 25000. From ²⁹ Si-NMR, (Me ₂ SiO _2/2 ) _0.90 (EpMeSiO _2/2 ) _0.10
The 3-glycidoxypropyl group content was 14 mol%, and the epoxy equivalent was 760 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) were used for GPC measurement. Moreover, the epoxy equivalent was calculated | required based on JISK-7236.

(Synthesis Example 2)
Dimethyldimethoxysilane (440 g) and 3-glycidoxypropyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise thereto, and after the addition was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and 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 = 2000, Mw = 3800, and (Me ₂ SiO _2/2 ) _0.83 (EpSiO _3/2 ) _0.17 from ²⁹ Si-NMR.
3-glycidoxypropyl group content is 22 mol%, epoxy equivalent is 550 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)
Dimethyldimethoxysilane (440 g) and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise thereto, and after the addition was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and 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 = 4800, and (Me ₂ SiO _2/2 ) _0.84 (EpSiO _3/2 ) _0.16 from ²⁹ Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 22 mol%, and the epoxy equivalent was 550 g / eq. Met.
The molecular weight and epoxy equivalent of polymer C were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 4)
Dimethyldimethoxysilane (400 g), trimethoxymethylsilane (100 g), and 3-glycidoxypropyltrimethoxysilane (100 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) 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 D. The molecular weight of the polymer D is Mn = 3200, Mw = 5400, and (Me ₂ SiO _2/2 ) _0.71 (MeSiO _3/2 ) _0.18 (EpSiO _3/2 ) _0.11 from ²⁹ Si-NMR.
3-glycidoxypropyl group content is 15 mol%, epoxy equivalent is 780 g / eq. Met.
The molecular weight and epoxy equivalent of polymer D were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 5)
In a separable flask equipped with a 2000 mL thermometer and a dropping device, dimethyldimethoxysilane (350 g), trimethoxymethylsilane (125 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (125 g) are placed at 50 ° C. Stir. Potassium hydroxide (1.2 g) / water (190 g) was slowly added dropwise thereto, and after completion of the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The polymer obtained was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer E. The molecular weight of the polymer E is Mn = 2900, Mw = 4600, and (Me ₂ SiO _2/2 ) _0.65 (MeSiO _3/2 ) _0.22 (EpSiO _3/2 ) _0.13 from ²⁹ Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 19 mol%, and the epoxy equivalent was 660 g / eq. Met.
The molecular weight and epoxy equivalent of polymer E were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 6)
Put a dimethyldimethoxysilane (400 g), trimethoxymethylsilane (50 g), tetramethoxysilane (50 g), 3-glycidoxypropyltrimethoxysilane (100 g) in a separable flask with a 2000 mL thermometer and dropping device. Stir at ° C. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) 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 F. The molecular weight of the polymer F is Mn = 2600, Mw = 3600. From ²⁹ Si-NMR, (Me ₂ SiO _2/2 ) _0.73 (MeSiO _3/2 ) _0.09 (EpSiO _3/2 ) _0.10 ( SiO _4/2 ) _0.08
The 3-glycidoxypropyl group content was 14 mol%, and the epoxy equivalent was 760 g / eq. Met.
The molecular weight and epoxy equivalent of polymer F were determined in the same manner as in Synthesis Example 1.

(Example 1)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corp., 5 g), 1,8-diazabicyclo (5.4.0) undecene -7 octylate (U-CAT SA 102, curing accelerator, San Apro, 0.5 g), PERHEXYL O (thermal radical polymerization initiator, Nippon Oil & Fats, 0.5 g), HOSTANOX O3 (phenolic) Compound, Clariant, 0.5 g) and sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) were 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. The obtained cured product was colorless and transparent visually.

(Example 2)
Polymer B (100 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corporation, 5 g), IRGACURE-250 (photocuring agent, manufactured by Ciba Specialty Chemicals, Inc., 0.5 g), IRGACURE-651 (photoradical polymerization initiator, Ciba Specialty Chemicals, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) -Defoaming was performed to obtain an encapsulant for optical semiconductor elements. The sealant was filled in a mold, and irradiated with ultraviolet rays at a strength of 100 mW / cm ² for 30 seconds using a high-pressure mercury lamp, to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 3)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corp., 5 g), 1,8-diazabicyclo (5.4.0) undecene -7 octylate (U-CAT SA 102, curing accelerator, San Apro, 0.5 g), IRGACURE-651 (photo radical polymerization initiator, Ciba Specialty Chemicals, 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant, 0.5 g) and sand stub P-EPQ (phosphorus compound, manufactured by Clariant, 0.5 g) were mixed and degassed to obtain an encapsulant for optical semiconductor elements. Obtained. After filling the mold with this sealant and irradiating it with ultraviolet light at an intensity of 100 mW / cm ² for 30 seconds using a high-pressure mercury lamp, it is cured at 100 ° C. × 3 hours, 130 ° C. × 3 hours, and has a thickness of 1 mm. A cured product was obtained. The obtained cured product was colorless and transparent visually.

Example 4
Polymer B (100 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corporation, 5 g), PERHEXYL O (thermal radical polymerization initiator, manufactured by NOF Corporation, 0.5 g), IRGACURE-250 (photocuring agent, Ciba Specialty Chemicals, 0.5 g), IRGACURE-651 (photo radical polymerization initiator, Ciba Specialty Chemicals, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, manufactured by Clariant, 0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealant is filled in a mold and cured at 100 ° C. for 3 hours, and then irradiated with ultraviolet light at a strength of 100 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain a cured product having a thickness of 1 mm. It was. The obtained cured product was colorless and transparent visually.

(Example 5)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corporation, 5 g), tetra-n-butylammonium butyltris-4-tert- Butylphenyl borate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and defoamed 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. The obtained cured product was colorless and transparent visually.

(Example 6)
Polymer A (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corp., 5 g), tetra-n-butylammonium butyltris-4-tert- Butylphenyl borate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and defoamed 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. The obtained cured product was colorless and transparent visually.

(Example 7)
Polymer C (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corporation, 5 g), tetra-n-butylammonium butyltris-4-tert- Butylphenyl borate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and defoamed 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. The obtained cured product was colorless and transparent visually.

(Example 8)
Polymer D (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corporation, 5 g), tetra-n-butylammonium butyltris-4-tert- Butylphenyl borate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and defoamed 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. The obtained cured product was colorless and transparent visually.

Example 9
Polymer E (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corp., 5 g), tetra-n-butylammonium butyltris-4-tert- Butylphenyl borate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and defoamed 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. The obtained cured product was colorless and transparent visually.

(Example 10)
Polymer F (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), FM7711 (acrylic modified silicone, manufactured by Chisso Corporation, 5 g), tetra-n-butylammonium butyltris-4-tert- Butylphenyl borate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and defoamed 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. The obtained cured product was colorless and transparent visually.

(Comparative Example 1)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), tetra-n-butylammonium butyl tris-4-tert-butylphenyl borate (BP3B, polymerization initiator, Showa Denko KK) Made, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g), mixed and defoamed. An encapsulant for optical semiconductor elements 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. The obtained cured product was colorless and transparent visually.

(Comparative Example 2)
Polymer B (100 g), methyl (meth) acrylate (acrylic compound, manufactured by Tokyo Chemical Industry Co., Ltd., 5 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), tetra-n-butylammonium butyltris- 4-tert-butylphenylborate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed and degassed to obtain a sealant 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. The obtained cured product was visually yellow.

(Comparative Example 3)
Celoxide 2021 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, 100 g), Ricacid MH-700G (manufactured by Shin Nippon Chemical Co., Ltd., 100 g), tetra-n-butylammonium butyltris-4-tert-butylphenylborate (BP3B, Polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) The mixture was mixed and defoamed 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. The cured product was colorless and transparent visually.

(Comparative Example 4)
YX-8000 (hydrogenated bisphenol A epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., 100 g), Ricacid MH-700G (manufactured by Shin Nippon Rika Co., Ltd., 64 g), tetra-n-butylammonium butyltris-4-tert-butylphenylborate (BP3B, polymerization initiator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ, (phosphorus compound, Clariant, 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. The cured product was reddish brown visually.

(Comparative Example 5)
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 in 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. The obtained cured product was colorless and transparent visually.

(Evaluation)
The following evaluation was performed about the composition produced in the Example and the comparative example, and its hardened | cured material. The results are shown in Table 1.

(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 at 100 mW / cm ² for 24 hours, and has a light transmittance of 400 nm. The measurement was performed using U-4000 manufactured by the company. 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 1500 hours, and a light transmittance of 400 nm was measured using U-4000 manufactured by Hitachi, Ltd. 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.

(4) Thermal cycle test (production of die bond material for optical semiconductor elements)
Flake silver powder (170 g) having an average particle size of 3 μm and a maximum particle size of 20 μm was added to polymer A (9 g) and polymer B (21 g), and the mixture was stirred and kneaded using a three roll.
Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 3.75 g) and U-CAT SA 102 (manufactured by Sun Apro Co., 0.075 g) were mixed and removed into the flaky silver powder-containing polymer (100 g). Foaming was performed to obtain a die bond material for optical semiconductor elements.

(Production of optical semiconductor element)
A light emitting element having a main light emission peak of 460 nm was mounted on a housing material with lead electrodes (PPA) using the produced die bonding material for an optical semiconductor element, and cured at 180 ° C. for 15 minutes to fix the light emitting element. Subsequently, the light-emitting element and the lead electrode are electrically connected with a gold wire, the composition prepared in the example and the comparative example is injected, and cured at 100 ° C. × 3 hours + 130 ° C. × 3 hours. Was made.

The produced optical semiconductor elements (20 pieces) were subjected to 3000 cycles of -30 ° C. for 30 minutes and 120 ° C. for 30 minutes to confirm the number of cracks and peeling from the housing material.

According to the present invention, light that is excellent in transparency, heat resistance, light resistance, and adhesion to a housing material, and can obtain a cured product that does not generate cracks or peeling even when subjected to a rapid thermal change due to a thermal cycle. The sealing agent for semiconductor elements and the optical semiconductor element using the same can be provided.

Claims (8)

A silicone resin having a cyclic ether-containing group in the molecule;
A compound having at least one radically polymerizable unsaturated group and at least one silane group in the molecule;
A curing agent that reacts with the cyclic ether-containing group;
A curable composition for optical semiconductor elements, comprising a polymerization initiator that reacts with the radically polymerizable unsaturated group. 0.1 to 20 parts by weight of a compound having at least one radical polymerizable unsaturated group and at least one silane group in the molecule with respect to 100 parts by weight of the silicone resin having a cyclic ether-containing group in the molecule The curable composition for optical semiconductor composition according to claim 1, which is contained. The curable composition for optical semiconductor elements according to claim 1, wherein the radical polymerizable unsaturated group is a (meth) acryl group. The curing agent that reacts with a cyclic ether-containing group is a thermosetting agent, and the polymerization initiator that reacts with a radically polymerizable unsaturated group is a thermal radical polymerization initiator. The curable composition for optical semiconductor elements described. The curing agent that reacts with a cyclic ether-containing group is a photocuring agent, and the polymerization initiator that reacts with a radically polymerizable unsaturated group is a photoradical polymerization initiator. Or the curable composition for optical semiconductor elements of 4. The curable composition for optical semiconductor elements according to claim 1, 2, 3, 4, or 5, wherein the curing agent that reacts with the cyclic ether-containing group is an acid anhydride. The curable composition for optical semiconductor elements according to claim 1, wherein the polymerization initiator that reacts with the radically polymerizable unsaturated group is a borate compound. An optical semiconductor element comprising the curable composition for optical semiconductor elements according to claim 1, 2, 3, 4, 5, 6 or 7.