JP2008189917A - Thermosetting composition for optical semiconductor, die bonding material for optical semiconductor element, underfill material for optical semiconductor element, sealant for optical semiconductor element and optical semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for an optical semiconductor excellent in mechanical strength, transparency, heat resistance and adhesion to a housing material etc. for a sealing optical semiconductor element of a cured article, a sealant for the optical semiconductor element and a die bonding material for the optical semiconductor element using the same, and the thermosetting composition for the optical semiconductor, the sealant for the optical semiconductor and the optical semiconductor element produced by using the die bonding material for the optical semiconductor element and/or an underfill material for the optical semiconductor element. <P>SOLUTION: This thermosetting composition for the optical semiconductor element comprises a silicone resin having one or more cyclic ether-containing group(s) in the molecule thereof, a thermal curing agent capable of reacting with the cyclic ether-containing group, and silicon oxide fine particles subjected to a surface treatment using an organic silicon-based compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a thermosetting composition for optical semiconductors that is excellent in mechanical strength, transparency, heat resistance of cured products, and adhesion to a housing material that encapsulates semiconductor elements, and an encapsulant for optical semiconductor elements using the same. , An optical semiconductor element die bond material, and an optical semiconductor thermosetting composition, an optical semiconductor sealant, an optical semiconductor element die bond material and / or an optical semiconductor element underfill material It relates to an element.

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

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

In addition, a sealing agent made of a conventional epoxy resin has advantages such as high adhesion and low moisture permeability, but has a problem that it has low light resistance to light of a short wavelength and is colored due to light deterioration. It was. In addition, the heat resistance was not sufficient.

On the other hand, in place of epoxy resin, a method is known in which a silicone resin having a high transmittance for light having a short wavelength in the blue to ultraviolet region is used as a sealant for sealing a light emitting element of an LED (for example, Patent Document 2). reference).
However, although silicone resin is excellent in heat resistance and light resistance, there is a problem that cracks are likely to occur after passing through a solder reflow furnace to mount an LED package or when a load such as a heat cycle is applied. .

The cause of the occurrence of such cracks is considered to be mainly due to insufficient mechanical strength of the cured product of the silicone resin. For such problems, for example, it is possible to increase the mechanical strength of a cured silicone resin by increasing the number of cross-linking points of the silicone resin. Such a cured product is a housing material that encloses a semiconductor element. In other words, problems such as a decrease in adhesiveness to heat and the like, and a decrease in heat resistance occur.

Another method for increasing the mechanical strength of the cured silicone resin is, for example, a method of adding inorganic fine particles to the silicone resin. However, in such a method, there existed a problem as optical semiconductor uses, such as LED, by the transparency fall of a silicone resin hardened | cured material, generation | occurrence | production of a void, etc.
JP 2003-277473 A JP 2002-314142 A

In view of the above situation, the present invention provides a thermosetting composition for optical semiconductors, which is excellent in mechanical strength, transparency, heat resistance of cured products, and adhesion to a housing material enclosing a light emitting device of a semiconductor device, and the like. Optical semiconductor element sealing agent, optical semiconductor element die-bonding material, and optical semiconductor thermosetting composition, optical semiconductor sealing agent, optical semiconductor element die-bonding material, and / or optical semiconductor element under An object of the present invention is to provide an optical semiconductor element using a fill material.

The present invention relates to a light containing silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and silicon oxide fine particles surface-treated with an organosilicon compound. It is a thermosetting composition for semiconductors.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have conducted surface treatment with a silicone resin having one or more cyclic ether-containing groups in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and an organosilicon compound. The resin composition containing fine silicon oxide particles is excellent in the mechanical strength of the cured product, does not generate cracks after passing through a solder reflow furnace, or under a load such as a heat cycle, and is transparent. Was found to be extremely excellent, and further, the heat resistance of the cured product and the adhesion to the light emitting element of the optical semiconductor element such as the light emitting diode were also excellent, and the present invention was completed. I came to let you.

The thermosetting composition for optical semiconductors of the present invention contains fine silicon oxide particles (hereinafter also referred to as finely divided silica) surface-treated with an organosilicon compound. The thermosetting composition for optical semiconductors of the present invention containing such finely divided silica is excellent in mechanical strength and transparency of the cured product.
That is, since the above-mentioned finely divided silica has an organosilicon compound on the surface of the silicon oxide fine particles, it has a highly lipophilic surface and is excellent in dispersibility in a highly lipophilic silicone resin described later. The excellent dispersibility of the finely divided silica contributes to the improvement of the mechanical strength of the cured product of the thermosetting composition for optical semiconductors of the present invention, and maintains high transparency by preventing the generation of voids and the like. Can be considered. In contrast, untreated silicon oxide fine particles that have not been surface-treated with an organosilicon compound have silanol groups on the surface, and thus have a highly hydrophilic surface and a highly lipophilic silicone described later. The resin composition containing the untreated silicon oxide fine particles is inferior in dispersibility to the resin, and is inferior in mechanical strength of the cured product, and has voids or the like at the interface between the silicon oxide fine particles and the resin. It is considered that the transparency was lowered due to the occurrence of light scattering caused by the generated silicon oxide fine particles not dispersed.

The silicon oxide fine particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, silica produced by a wet method such as colloidal silica, sol-gel silica, and precipitated silica. It is done. Among these, fumed silica that has a small amount of volatile components and provides high transparency is preferably used.

Although it does not specifically limit as a magnitude | size of the said silicon oxide microparticles | fine-particles, the preferable minimum of a primary particle diameter is 5 nm, and a preferable upper limit is 200 nm. When it is less than 5 nm, the dispersibility of fine silica obtained by surface-treating the silicon oxide fine particles with an organosilicon compound is lowered, and the transparency of the cured product of the thermosetting composition for optical semiconductors of the present invention is inferior. There is. If it exceeds 200 nm, light scattering caused by finely divided silica obtained by surface-treating silicon oxide fine particles with an organosilicon compound is likely to occur, and the transparency of the cured product of the thermosetting composition for optical semiconductors of the present invention is improved. May decrease. A more preferred lower limit is 8 nm, and a more preferred upper limit is 150 nm. The primary particle diameter of the silicon oxide fine particles means an average value of the diameter when the silicon oxide fine particles are spherical, and an average value of the long diameter when the silicon oxide fine particles are non-spherical.

In the thermosetting composition for optical semiconductors of the present invention, the silicon oxide fine particles are surface-treated with an organosilicon compound.
The organosilicon compound is not particularly limited, and examples thereof include a silane compound having an alkyl group, a silicon compound having a siloxane skeleton such as dimethylsiloxane, a silicon compound having an amino group, and a silicon having a (meth) acryl group. Examples thereof include silicon compounds and silicon compounds having an epoxy group. In addition, the said (meth) acryl means acryl or methacryl.

The organosilicon compound is preferably a compound that is chemically bonded to the surface of the silicon oxide fine particles, and in particular, an alkyl having a structure represented by the following general formula (17), (18), or (19) A group-containing silane compound is preferred.

In the general formulas (17) and (18), R represents an alkyl group having 1 to 3 carbon atoms, and in the general formula (19), R 'represents an alkyl group having 4 to 8 carbon atoms.

As shown in FIGS. 4 (a), (b) and (c), the alkyl group-containing silane compound having the structure represented by the general formulas (17), (18) and (19) contains an alkyl group. Bonds other than the alkyl group represented by R or R ′ of the silicon atom in the silane compound 41, 42 or 43 react with the silanol group on the surface of the silicon oxide fine particle 40 to form a chemical bond. It is what you are doing. 4A, 4B, and 4C show that the alkyl group-containing silane compound having the structure represented by the general formulas (17), (18), and (19) is formed on the surface of the silicon oxide fine particles. It is sectional drawing which shows the state which couple | bonded like a test plot.

In the thermosetting composition for optical semiconductors of the present invention, the organosilicon compound for surface-treating the silicon oxide fine particles is an alkyl group-containing silane compound having a structure represented by the general formula (17) or (18). If so, the finely divided silica is excellent in dispersibility in the silicone resin described later, and the thermosetting composition for optical semiconductors of the present invention has the mechanical strength, transparency, heat resistance and housing of the cured product. Excellent adhesion to materials and the like. Moreover, it is preferable because the fine silica can be highly filled while maintaining the viscosity of the thermosetting composition for optical semiconductors of the present invention at a desired value. In the general formula (17) or (18), R is 1 for the lower limit of the carbon number and 3 for the upper limit. When it exceeds 3, the said organosilicon type compound may raise | generate heat resistance deterioration, and the heat resistance of the thermosetting composition for optical semiconductors of this invention may fall.

Further, when the organosilicon compound for surface treatment of the silicon oxide fine particles is an alkyl group-containing silane compound having a structure represented by the general formula (19), the finely divided silica is used in a silicone resin described later. It becomes excellent in dispersibility, and the thermosetting composition for optical semiconductors of the present invention has excellent mechanical strength, transparency, heat resistance, and adhesion to a housing material and the like of the cured product. In the general formula (19), R ′ has a lower limit of 4 carbon atoms and an upper limit of 8. When it is less than 4, the dispersibility in the thermosetting composition for optical semiconductors of the present invention containing the silicone resin described later of the fine silica is insufficient, and the thermosetting composition for optical semiconductors of the present invention is insufficient. There may be a problem that the transparency of the cured product cannot be ensured. When it exceeds 8, the said organosilicon compound may cause heat-resistant deterioration, and the heat resistance of the thermosetting composition for optical semiconductors of this invention may fall.

From the viewpoint of heat resistance, the organosilicon compound for surface-treating the silicon oxide fine particles is more preferably the general formula (17) or (18).

The alkyl group-containing silane compound having the structure represented by the general formula (17), that is, the compound that is bonded to the surface of the silicon oxide fine particles as shown in FIG. 4 (a) is not particularly limited. It is preferable that it is a compound which has, specifically, dimethylsilyl dichloride, dimethyldimethoxysilane etc. are mentioned, for example.

Further, the alkyl group-containing silane compound having the structure represented by the general formula (18), that is, the compound in which the state bonded to the surface of the silicon oxide fine particles is as shown in FIG. It is preferable that it is a compound which has this, and, specifically, a hexamethyldisilazane, a trimethylsilyl chloride, trimethylmethoxysilane etc. are mentioned, for example.

Further, the alkyl group-containing silane compound having the structure represented by the general formula (19), that is, the compound in which the state bonded to the surface of the silicon oxide fine particles is as shown in FIG. Examples include octylsilane trichloride and octyltrimethoxysilane.

The silicon oxide fine particles (fine powder silica) surface-treated with the organosilicon compound have a preferred lower limit of BET specific surface area of 30 m ² / g and a preferred upper limit of 400 m ² / g. If it is less than 30 m ² / g, light scattering caused by the fine powder silica occurs in the cured product of the thermosetting composition for optical semiconductors of the present invention, and it is difficult to ensure the transparency of the cured product. Become. When it exceeds 400 m ² / g, the dispersibility in the thermosetting composition for optical semiconductors of the present invention is poor, and the mechanical strength and transparency of the cured product of the thermosetting composition for optical semiconductors of the present invention are poor. May be sufficient. A more preferable lower limit is 50 m ² / g, and a more preferable upper limit is 350 m ² / g.

In the fine silica, the ratio of the organosilicon compound to the silicon oxide fine particles is not particularly limited, but the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 15 parts by weight with respect to 100 parts by weight of the silicon oxide fine particles. It is. If the amount is less than 0.1 parts by weight, the surface treatment of the silicon oxide fine particles with the organosilicon compound becomes insufficient, and the dispersibility of the fine silica in the thermosetting composition for optical semiconductors of the present invention decreases. The mechanical strength and transparency of the cured product may be insufficient. If it exceeds 15 parts by weight, a large amount of the organosilicon compound that does not react with the fine silica surface may remain, resulting in deterioration of heat resistance or reduction of film thickness.

The method for treating the surface of the silicon oxide fine particles with the organosilicon compound is not particularly limited. For example, the silicon oxide fine particles are added to a mixer capable of high-speed stirring such as a Henschel mixer and a V-type mixer while stirring. A dry method in which an organosilicon compound is added directly or as an alcohol aqueous solution, an organic solvent solution or an aqueous solution, a slurry method in which an organosilicon compound is added to a slurry of silicon oxide fine particles, and a step of drying the silicon oxide fine particles Direct treatment method such as spray method for spraying an organosilicon compound; organosilicon during mixing of silicon oxide fine particles and a matrix resin such as a silicone resin described later in preparing the thermosetting composition for optical semiconductors of the present invention Examples include an integral blend method in which a system compound is directly added.

In the thermosetting composition for optical semiconductors of the present invention, the content of the fine silica is not particularly limited, but a silicone resin to be described later (when a bifunctional silicone resin to be described later is contained, the silicone resin and the bifunctional silicone resin to be described later) The preferred lower limit is 1 part by weight and the preferred upper limit is 50 parts by weight with respect to 100 parts by weight. When the amount is less than 1 part by weight, the mechanical strength of the cured product of the thermosetting composition for optical semiconductors of the present invention may be insufficient, and the occurrence of cracks may not be sufficiently prevented. The viscosity of the thermosetting composition for optical semiconductors of the present invention is increased. For example, when used as a sealing agent for optical semiconductor elements such as LEDs, the problem of foaming may occur in the filling process, and voids May occur and the transparency of the cured product may decrease. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 40 parts by weight.

Moreover, it is preferable that the said fine powder silica is not aggregated in the thermosetting composition for optical semiconductors of this invention, and is disperse | distributing in the state close | similar to a primary particle. The state close to the primary particles means that the fine silica is not necessarily completely dispersed as primary particles in the thermosetting composition for optical semiconductors of the present invention, and is agglomerated or aggregated to some extent. It means that it may exist as particles.
When the fine silica is present as the lump particle, a preferable upper limit of the average diameter of the lump particle is 200 nm. If it exceeds 200 nm, light scattering due to the fine silica is generated, and the transparency of the cured product may be insufficient. A more preferred upper limit is 150 nm. In addition, the average diameter of the said lump particle means the average value of the long diameter of the fine powder silica group (lump particle) which exists by aggregation etc.

In the thermosetting composition for optical semiconductors of the present invention, the silicone resin preferably has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

In the general formula (1) and ^(2), R 1, ^{R 2} and ^{R 3} is at least one represents a cyclic ether-containing group, ^R 1, ^{R 2} and ^{R 3} other than the cyclic ether-containing group, the carbon Represents a hydrocarbon of formula 1 to 8 or a fluorinated product thereof, which may be the same or different from each other, and furthermore, in the repeating structure in the silicone resin skeleton, a plurality of different types of R ¹ , R ² and R ³ may be contained.

Further, when the total number of structural units contained in the silicone resin is 1, the lower limit of the content of the structural unit represented by the general formula (1) is 0.6, and the upper limit is 0.95 (molar conversion). The lower limit of the content of the structural unit represented by the general formula (2) is 0.05, and the upper limit is 0.4 (in terms of mole). The light of the present invention contains a silicone resin having a cyclic ether-containing group and containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the above range. The thermosetting composition for semiconductors has a high transmittance with respect to light having a short wavelength in the blue to ultraviolet region, and when used as a sealing agent for an optical semiconductor element, heat generation of the light-emitting element to be sealed and film reduction due to light emission or There is no discoloration and excellent heat resistance and light resistance, and when the light emitting element of an optical semiconductor element such as a light emitting diode is sealed, the optical semiconductor element has excellent adhesion to a housing material or the like.

In the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), at least one of R ^{1 to} R ³ represents a cyclic ether-containing group. In the present specification, the cyclic ether-containing group only needs to contain a cyclic ether group as at least a part of the group. For example, the cyclic ether-containing group contains another skeleton such as an alkyl group or an alkyl ether group and a cyclic ether group. Means a good 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.
Moreover, the said silicone resin may contain several different types of R < ¹ >, R < ² > and R < ³ > in the repeating structure in silicone resin frame | skeleton, respectively. It is sufficient that both the structural unit represented by the above (1) and the structural unit represented by the above general formula (2) are contained in the skeleton as components, and the plurality of repeated structural units are not necessarily the same. It means that it may not be a repeating unit.

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 lower limit of the content of the cyclic ether-containing group is 5 mol%, and the upper limit is 40 mol%. If it is less than 5 mol%, the reactivity between the silicone resin and the thermosetting agent described later is remarkably lowered, and the curability of the photocurable semiconductor thermosetting composition of the present invention becomes insufficient. If it exceeds 40 mol%, the number of cyclic ether-containing groups not involved in the reaction between the silicone resin and the thermosetting agent will increase, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention will decrease. A preferable lower limit is 7 mol%, and a preferable upper limit is 30 mol%.
In the present specification, the content of the cyclic ether-containing group means the amount of the cyclic ether-containing group contained in the average composition of the silicone resin component.

In the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), R ^{1 to} R ³ other than the cyclic ether-containing group are carbon atoms having 1 to 8 carbon atoms. Represents hydrogen or a fluoride thereof.

It does not specifically limit as said C1-C8 hydrocarbon, For example, a methyl group, an 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 silicone resin, the structural unit represented by the general formula (1) (hereinafter also referred to as a bifunctional structural unit) is a structure represented by the following general formula (1-2), that is, in the bifunctional structural unit. One of the oxygen atoms bonded to the silicon atom is a structure in which a hydroxyl group or an alkoxy group is formed.
(R ¹ R ² 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, the structural unit represented by the general formula (2) (hereinafter also referred to as trifunctional structural unit) is a structure represented by the following general formula (2-2) or (2-3). That is, a structure in which two of the oxygen atoms bonded to the silicon atom in the trifunctional structural unit each constitute a hydroxyl group or an alkoxy group, or one of the oxygen atoms bonded to the silicon atom in the trifunctional structural unit is a hydroxyl group Or the structure which comprises an alkoxy group is included.
(R ³ SiX ₂ O _1/2 ) (2-2)
(R ³ SiXO _2/2 ) (2-3)
In the general formulas (2-2) and (2-3), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the general formulas (1-2), (2-2), and (2-3), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited. Group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

When the above-mentioned silicone resin is subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation is observed depending on the type of substituent, the general formula (1 ) And (1-2) corresponding to bifunctional structural units appear in the vicinity of −10 to −30 ppm, and the trifunctional structural units of the above general formulas (2), (2-2) and (2-3) Each peak corresponding to appears in the vicinity of −50 to −70 ppm.
Therefore, it is possible to measure the ratio of the silicone resin 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 bifunctional structural unit of the general formula (1), not only the ²⁹ Si-NMR measurement result but also ¹ H-NMR The ratio of structural units can be discriminated by using the results measured by ¹⁹ F-NMR or the like as necessary.

It is preferable that an average composition formula of such a silicone resin mainly composed of a bifunctional structural unit and a trifunctional structural unit is represented by the following general formula (3), (4) or (5). In addition, the said silicone resin has an average composition formula represented by the following general formula (3), (4) or (5) that the thermosetting composition for optical semiconductors of this invention is the following general formula. (3) Not only when it contains only the resin component represented by (4) or (5), but when it is a mixture containing resin components of various structures, the average composition of the resin components contained This also means the case represented by the following general formula (3), (4) or (5).

一般式（３）中、ａ、ｂは、ａ／（ａ＋ｂ）＝０．６〜０．９５、ｂ／（ａ＋ｂ）＝０．０５〜０．４を満たし、Ｒ^４〜Ｒ^６のいずれかが環状エーテル含有基であり、環状エーテル含有基以外のＲ^４〜Ｒ^６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 (3), a and b satisfy a / (a + b) = 0.6 to 0.95, b / (a + b) = 0.05 to 0.4, and any one of R ^{4 to} R ⁶ Is a cyclic ether-containing group, and R ^{4 to} R ⁶ other than the cyclic ether-containing group are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, which may be the same or different from each other. .

一般式（４）中、ｃ、ｄ、ｅは、（ｃ＋ｄ）／（ｃ＋ｄ＋ｅ）＝０．６〜０．９５、ｅ／（ｃ＋ｄ＋ｅ）＝０．０５〜０．４を満たし、Ｒ^７〜Ｒ^１１のいずれかが環状エーテル含有基であり、環状エーテル含有基以外のＲ^７〜Ｒ^１１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^７Ｒ^８ＳｉＯ_２／２）と（Ｒ^９Ｒ^１１ＳｉＯ_２／２）とは構造が異なるものである。

In general formula (4), c, d, and e satisfy (c + d) / (c + d + e) = 0.6 to 0.95, e / (c + d + e) = 0.05 to 0.4, and R ^{7 to} R ¹¹ is a cyclic ether-containing group, and R ^{7 to} R ¹¹ other than the cyclic ether-containing group are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, which may be the same as or different from each other. It may be. However, (R ⁷ R ⁸ SiO _2/2 ) and (R ⁹ R ¹¹ SiO _2/2 ) have different structures.

一般式（５）中、ｆ、ｇ、ｈは、ｆ／（ｆ＋ｇ＋ｈ）＝０．６〜０．９５、（ｇ＋ｈ）／（ｆ＋ｇ＋ｈ）＝０．０５〜０．４を満たし、Ｒ^１２〜Ｒ^１５のいずれかが環状エーテル含有基であり、環状エーテル含有基以外のＲ^１２〜Ｒ^１５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^１４ＳｉＯ_３／２）と（Ｒ^１５ＳｉＯ_３／２）とは構造が異なるものである。

In general formula (5), f, g, and h satisfy f / (f + g + h) = 0.6 to 0.95, (g + h) / (f + g + h) = 0.05 to 0.4, and R ^{12 to} R ¹⁵ is a cyclic ether-containing group, and R ^{12 to} R ¹⁵ other than the cyclic ether-containing group are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, which may be the same as or different from each other. It may be. However, (R ¹⁴ SiO _3/2 ) and (R ¹⁵ SiO _3/2 ) have different structures.

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.

Moreover, it is preferable that the said silicone resin has a cyclic ether containing group in the structural unit represented by the said General formula (2), ie, a trifunctional structural unit. When the cyclic ether-containing group is contained in the trifunctional structure, the cyclic ether-containing group is likely to be exposed outside the polysiloxane skeleton of the silicone resin, and the cured product of the thermosetting composition for optical semiconductors of the present invention is sufficient. Taking a three-dimensional cross-linking structure makes the heat resistance sufficient, and it is possible to suitably prevent film loss in the cured product.

Specifically, the silicone resin in which the cyclic ether-containing group is bonded to a trifunctional structural unit is preferably represented by, for example, the following average formula (6), (7), or (8). .

一般式（６）中、ｉ、ｊは、ｉ／（ｉ＋ｊ）＝０．６〜０．９５、ｊ／（ｉ＋ｊ）＝０．０５〜０．４を満たし、Ｒ^１８が環状エーテル含有基であり、Ｒ^１６、Ｒ^１７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 (6), i and j satisfy i / (i + j) = 0.6 to 0.95, j / (i + j) = 0.05 to 0.4, and R ¹⁸ is a cyclic ether-containing group. R ¹⁶ and R ¹⁷ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different from each other.

一般式（７）中、ｋ、ｌ、ｍは、（ｋ＋ｌ）／（ｋ＋ｌ＋ｍ）＝０．６〜０．９５、ｍ／（ｋ＋ｌ＋ｍ）＝０．０５〜０．４を満たし、Ｒ^２３が環状エーテル含有基であり、Ｒ^１９〜Ｒ^２２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^１９Ｒ^２０ＳｉＯ_２／２）と（Ｒ^２１Ｒ^２２ＳｉＯ_２／２）とは構造が異なるものである。

In the general formula (7), k, l, m are, (k + l) / ( k + l + m) = 0.6~0.95, satisfies the m / (k + l + m ) = 0.05~0.4, R 23 is annular It is an ether-containing group, and R ^{19 to} R ²² are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different. However, (R ¹⁹ R ²⁰ SiO _2/2 ) and (R ²¹ R ²² SiO _2/2 ) have different structures.

一般式（８）中、ｎ、ｏ、ｐは、ｎ／（ｎ＋ｏ＋ｐ）＝０．６〜０．９５を満たし、（ｏ＋ｐ）／（ｎ＋ｏ＋ｐ）＝０．０５〜０．４を満たし、Ｒ^２６が環状エーテル含有基であり、Ｒ^２４、Ｒ^２５、Ｒ^２７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 (8), n, o, and p satisfy n / (n + o + p) = 0.6 to 0.95, satisfy (o + p) / (n + o + p) = 0.05 to 0.4, and R ²⁶ Is a cyclic ether-containing group, and R ²⁴ , R ²⁵ and R ²⁷ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different.

If the silicone resin is composed mainly of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), structural units other than these structural units may be used. You may have. In this case, when the total number of structural units contained in the silicone resin is 1, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) A preferred lower limit is 0.9 (molar conversion). If it is less than 0.9 (in terms of mole), the effects such as excellent heat resistance, light resistance, and high adhesion of the thermosetting composition for optical semiconductors of the present invention may be significantly impaired. A more preferred lower limit is 0.95 (molar conversion).

The structural unit other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) that may be contained in the silicone resin is not particularly limited. The structural unit represented by (9) or chemical formula (10) is mentioned.

一般式（９）中、Ｒ^２８、Ｒ^２９及びＲ^３０は、環状エーテル含有基、又は、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。

In the general formula (9), R ²⁸ , R ²⁹ and R ³⁰ represent a cyclic ether-containing group, a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as each other, May be different.

In the case where the silicone resin contains a structural unit represented by the general formula (9) or the chemical formula (10), these contents include the structural unit represented by the general formula (1) and the general formula There is no particular limitation as long as the total content of the structural units represented by (2) falls within the above-described range. For example, when the total number of structural units contained in the silicone resin is 1, The upper limit with preferable content of the structural unit represented by General formula (9) is 0.1 (mol conversion). The upper limit with preferable content of the structural unit represented by the said Chemical formula (10) is 0.1 (mol conversion). When content of the structural unit represented by the said General formula (9) exceeds 0.1 (mol conversion), the heat resistance of the thermosetting composition for optical semiconductors of this invention may fall. Moreover, when the content of the structural unit represented by the chemical formula (10) exceeds 0.1, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention, It may be difficult to maintain adhesion.

The structural unit represented by the general formula (9) (hereinafter also referred to as a tetrafunctional structural unit) is represented by the following general formula (9-2), (9-3) or (9-4). A structure, 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 one of oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit One of which constitutes a hydroxyl group or an alkoxy group.
(SiX ₃ O _1/2 ) (9-2)
(SiX ₂ O _2/2 ) (9-3)
(SiXO _3/2 ) (9-4)
In the general formulas (9-2), (9-3), and (9-4), 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 (9-2) to (9-4), 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 thermosetting composition for optical semiconductors of the present invention, the silicone resin preferably contains an alkoxy group in a range where the lower limit is 0.5 mol% and the upper limit is 10 mol%. By containing such an alkoxy group, the heat resistance and light resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention are dramatically improved. This is presumably because the curing rate can be drastically improved by containing an alkoxy group in the silicone resin, thereby preventing thermal deterioration during curing.
In addition, since the curing speed is dramatically improved as described above, sufficient curability can be obtained even with a relatively small addition amount when a curing accelerator is added.

When the content of the alkoxy group is less than 0.5 mol%, the curing rate may not be sufficiently obtained and the heat resistance may be deteriorated. When the content exceeds 10 mol%, the silicone resin or the optical semiconductor of the present invention is used. The storage stability of the thermosetting composition is deteriorated and the heat resistance is deteriorated. A more preferred lower limit is 1 mol%, and a more preferred upper limit is 5 mol%.
In addition, in this specification, content of the said alkoxy group means the quantity of the alkoxy group contained in the average composition of the said silicone resin.

Moreover, it is preferable that the said silicone resin 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 of the resin composition is 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. For example, (1) a substituent is introduced by a hydrosilylation reaction between a silicone resin (a) having a SiH group and a vinyl compound having a cyclic ether-containing group. Examples thereof include (2) a method in which an alkoxysilane compound and an alkoxysilane compound having a cyclic ether-containing group are subjected to a condensation reaction.

In the above method (1), the hydrosilylation reaction is a method of reacting a SiH group and a vinyl group in the presence of a catalyst as necessary.

The silicone resin (a) having a SiH group is preferably represented by the general formula (1) described above after reacting a vinyl compound having a SiH group in the molecule and having the cyclic ether-containing group. A structure having a structural unit and a structural unit represented by the general formula (2) as a main component, more preferably, an average composition formula is a structure represented by any one of the above general formulas (6) to (8). The thing is mentioned.

The vinyl compound having a cyclic ether-containing group is not particularly limited as long as it is a vinyl compound having one or more cyclic ether-containing groups in the molecule. For example, vinyl diglycidyl ether, allyl glycidyl ether, glycidyl (meth) Examples thereof include acrylate, butadiene monooxide, vinylcyclohexene oxide, and allylcyclohexene oxide. In addition, the said (meth) acryl means acryl or methacryl.

Examples of the catalyst used as necessary during the hydrosilylation reaction include, for example, a simple substance of Group 8 metal, a metal solid supported on a carrier such as alumina, silica, carbon black, and the like. Examples include salts and complexes. Specifically, as the metal of Group 8 of the periodic table, for example, platinum, rhodium, and ruthenium are preferable, and platinum is particularly preferable.
As the hydrosilation reaction catalyst using platinum, for example, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complex, platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, And dicarbonyldichloroplatinum.

Although it does not specifically limit as reaction conditions at the time of the said hydrosilylation reaction, when the reaction temperature and the yield are considered, the preferable minimum is 10 degreeC and a preferable upper limit is 200 degreeC. A more preferred lower limit is 30 ° C., a more preferred upper limit is 150 ° C., a still more preferred lower limit is 50 ° C., and a still more preferred upper limit is 120 ° C.

Moreover, the said hydrosilylation reaction may be performed without a solvent and may be performed using a solvent.
The solvent is not particularly limited, and examples thereof include ether solvents such as dioxane, tetrahydrofuran and propylene glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; hydrocarbon solvents such as toluene, xylene and cyclohexane; acetic acid Examples include ester solvents such as ethyl and butyl acetate; alcohol solvents such as butyl cellosolve and butyl carbitol. Of these, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents are preferred. Specifically, dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate are particularly preferred because of the solubility of the raw materials and the solvent recoverability. preferable.

In the said method (2), as an alkoxysilane compound, the alkoxysilane which has a siloxane unit of the following general formula (11), (12), or its partial hydrolyzate is mentioned, for example.

In the general formulas (11) and (12), R ^{31 to} R ³³ represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched carbon having 1 to 4 carbon atoms. Represents an alkoxy group.

In the general formulas (11) and (12), when R ^{31 to} R ³³ are 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, An isohexyl group, a cyclohexyl group, a phenyl group, etc. are mentioned.

In the general formulas (11) and (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, or n -Propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

Specific examples of the compound represented by the general formula (11) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, isopropyl (methyl) dimethoxysilane, and cyclohexyl (methyl). Examples include dimethoxysilane and methyl (phenyl) dimethoxysilane.

Specific examples of the compound represented by the general formula (12) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane. And phenyltrimethoxysilane.

In the alkoxysilane compound, the compounding ratio of the alkoxysilane having a siloxane unit represented by the general formulas (11) and (12) or a partial hydrolyzate thereof is condensed with an alkoxysilane compound having a cyclic ether-containing group, which will be described later. The silicone resin synthesized by reaction preferably has a structure having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), more preferably the general formula (6). ) To (8), so that the structure is represented as appropriate.

Examples of the alkoxysilane 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), when R ³⁴ and / or R ³⁵ and R ³⁶ are cyclic ether groups, and only one of R ³⁴ or R ³⁵ is a cyclic ether group, The other represents a 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 the general formulas (13) and (14), the cyclic ether-containing group represented by R ³⁴ and / or R ³⁵ , R ³⁶ is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Can be 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 either R ³⁴ or R ³⁵ is a hydrocarbon 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, An isohexyl group, a cyclohexyl group, a phenyl group, etc. are mentioned.

Further, in the general formulas (13) and (14), 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.

Specific examples of the compound represented by the general formula (13) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidide. Xylpropyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl ( And methyl) diethoxysilane.

Specific examples of the compound represented by the general formula (14) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

In the method (2), as a specific method for the condensation reaction of the alkoxysilane compound and the alkoxysilane compound having a cyclic ether-containing group, for example, the alkoxysilane compound and the alkoxysilane compound having a cyclic ether-containing group can be used. And a method of synthesizing a silicone resin by reacting in the presence of water and an acid or basic catalyst.
Alternatively, the alkoxysilane compound may be reacted in advance in the presence of water and an acid or basic catalyst, and then the alkoxysilane compound having a cyclic ether-containing group may be reacted.

In the method (2), when the alkoxysilane compound and the alkoxysilane compound having a cyclic ether-containing group are reacted in the presence of water and an acid or a basic catalyst, the alkoxysilane having the cyclic ether-containing group. The compound of the cyclic ether-containing group contained in the average composition of the silicone resin component synthesized by condensation reaction of the cyclic ether-containing group with the alkoxysilane compound preferably having the alkoxysilane compound and the cyclic ether-containing group. It mix | blends so that the minimum of quantity may be 5 mol% and an upper limit may be 40 mol%.

The 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 alkoxysilane compound having the cyclic ether-containing group, and is appropriately adjusted.

The acidic catalyst is a catalyst for reacting the alkoxysilane compound with an alkoxysilane compound having a cyclic ether-containing group, for example, inorganic acids such as phosphoric acid, boric acid, carbonic acid; formic acid, acetic acid, propionic acid, Organic acids such as 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; these acid anhydrides or derivatives, etc. Can be mentioned.

The basic catalyst is a catalyst for reacting the alkoxysilane compound with an alkoxysilane compound having a cyclic ether-containing group. For example, hydroxylation of an alkali metal such as sodium hydroxide, potassium hydroxide, cesium hydroxide, etc. Alkali metal alkoxides such as sodium-t-butoxide, potassium-t-butoxide, cesium-t-butoxide; alkali metal silanol compounds such as sodium silanolate compounds, potassium silanolate compounds, cesium silanolate compounds, etc. It is done. 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 preferable lower limit is 10 ppm and the preferable upper limit is 10,000 ppm with respect to the total amount of the alkoxysilane compound and the alkoxysilane compound having a cyclic ether-containing group. Yes, 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 being dissolved in water or the alkoxysilane compound.

The condensation reaction between the alkoxysilane compound and the alkoxysilane compound having a cyclic ether-containing group may be carried out without a solvent or may be carried out using a 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.

As a method for synthesizing the silicone resin, the method (2) is preferable from the viewpoint of adjusting the amount of alkoxy groups.
In order to bring the alkoxy group into an appropriate range, the above method (2) 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 thermal constituent composition for optical semiconductors of the present invention preferably contains a bifunctional silicone resin having one or more cyclic ether-containing groups in the molecule.
By blending such a bifunctional silicone resin, the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention is significantly improved. This is because, in the cured product, the bifunctional silicone resin having 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. It is guessed that this is because it enters.

The cyclic ether-containing group of the bifunctional silicone resin only needs to contain a cyclic ether group in at least a part of the group, for example, it contains another skeleton such as an alkyl group or an alkyl ether group and a cyclic ether group. Means a group which may be

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, and a glycidyl group is more 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.

The bifunctional silicone resin having one or more such cyclic ether-containing groups in the molecule is not particularly limited, but contains a resin component whose average composition formula is represented by the following general formula (15) or (16). Is preferred. 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. In other words, 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 ( 15) or the case where only the resin component represented by (16) is contained, and in the case of a mixture containing resin components having various structures, the following general formula It also means the case represented by (15) or (16).

一般式（１５）中、Ｒ^３９及び／又はＲ^４０は、環状エーテル含有基であり、Ｒ^３７、Ｒ^３８は、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^３９又はＲ^４０のいずれか一方のみが環状エーテル含有基である場合、他方は、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、ｒ／（ｒ＋ｓ）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、ｓ／（ｒ＋ｓ）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 ³⁹ and / or R ⁴⁰ is a cyclic ether-containing group, R ³⁷ and R ³⁸ represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other May be different. When only one of R ^{39 and} R ⁴⁰ is a cyclic ether-containing group, the other represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit for r / (r + s) 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 s / (r + s) 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^４５及び／又はＲ^４６は、環状エーテル含有基であり、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４は、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^４５又はＲ^４６のいずれか一方のみが環状エーテル含有基である場合、他方は、炭素数１〜８の炭化水素或いはそのフッ素化物を表し、（Ｒ^４１Ｒ^４２ＳｉＯ_２／２）と（Ｒ^４３Ｒ^４４ＳｉＯ_２／２）とは構造が異なるものである。
また、ｔ＋ｕ／（ｔ＋ｕ＋ｖ）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、ｖ／（ｔ＋ｕ＋ｖ）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 ⁴⁵ and / or R ⁴⁶ is a cyclic ether-containing group, and R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. Further, when only one of R ^{45 and} R ⁴⁶ is a cyclic ether-containing group, the other represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and (R ⁴¹ R ⁴² SiO _2/2 ) and (R ⁴³ R ⁴⁴ SiO _2/2 ) is different in structure.
The preferred lower limit of t + u / (t + u + v) 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 v / (t + u + v) 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.

In the bifunctional silicone resin, the bifunctional structural unit has a structure represented by the following general formula (1-2), that is, one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit is a hydroxyl group or an alkoxy group. The structure which comprises is included.
(R ¹ R ² 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 general formula (1-2), 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, an n-propoxy group, an n-butoxy group, An isopropoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, etc. are mentioned.

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.

A method for synthesizing such a bifunctional silicone resin is not particularly limited, and examples thereof include a method similar to the method for synthesizing the above-described silicone resin. That is, a method of introducing a substituent by a hydrosilylation reaction between a silicone resin (b) having a SiH group and a vinyl compound having a cyclic ether-containing group (method (3)), an alkoxysilane compound and a cyclic ether-containing group. The method (method (4)) etc. which carry out a condensation reaction with the alkoxysilane compound which has are mentioned.

When synthesizing a bifunctional silicone resin by the above method (3), the silicone resin (b) having the SiH group, for example, reacts with a vinyl compound containing a SiH group in the molecule and having the cyclic ether-containing group. After making it, what will become a structure represented by the general formula (15) or (16) mentioned above is mentioned.

The vinyl compound having a cyclic ether-containing group is not particularly limited as long as it is a vinyl compound having one or more cyclic ether-containing groups in the molecule. For example, vinyl diglycidyl ether, allyl glycidyl ether, glycidyl (meth) Examples thereof include acrylate, butadiene monooxide, vinylcyclohexene oxide, and allylcyclohexene oxide. In addition, the said (meth) acryl means acryl or methacryl.

Moreover, at the time of the above hydroshell relation reaction, as in the case of synthesizing the above-mentioned silicone resin, a catalyst may be used as necessary, or it may be carried out without a solvent, or using a solvent. Also good.

When synthesizing the bifunctional silicone resin by the method (4), the alkoxysilane compound is not particularly limited, and examples thereof include the same compounds as the dialkoxysilane compound of the general formula (11) described above.
Moreover, as an alkoxysilane compound which has the said cyclic ether containing group, the thing similar to the dialkoxysilane compound of General formula (13) mentioned above is mentioned, for example.

Specific examples of the compound represented by the general formula (11) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, isopropyl (methyl) dimethoxysilane, and cyclohexyl (methyl). Examples include dimethoxysilane and methyl (phenyl) dimethoxysilane.

Specific examples of the compound represented by the general formula (13) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidide. Xylpropyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl ( And methyl) diethoxysilane.

Specific examples of the condensation reaction between the alkoxysilane compound and the alkoxysilane compound having a cyclic ether-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 in the case of reacting with 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 thermosetting composition for optical semiconductors of this invention contains the thermosetting agent which can react with the said cyclic ether containing group.
The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group of the silicone resin. For example, 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, mercaptans such as mercaptopropionic acid esters, terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ) Methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, bromine Phenolic resins such as bisphenol A novolac; polyols obtained by hydrogenating aromatic rings of these phenolic resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydride Phthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic 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 3-alkylglutaric anhydride having an optionally branched alkyl group having 1 to 8 carbon atoms, such as alicyclic acid anhydrides, 3-methylglutaric anhydride, etc., 2-ethyl-3- 2,3-dialkylglutaric anhydride, 2,4-diethylglutar having a C1-C8 alkyl group which may be branched, such as propylglutaric anhydride Alkyl-substituted glutaric anhydrides such as 2,4-dialkylglutaric anhydride having an alkyl group having 1 to 8 carbon atoms which may be branched, such as anhydride, 2,4-dimethylglutaric anhydride, anhydrous Aromatic acid anhydrides such as phthalic acid, trimellitic anhydride, pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and salts thereof, the above aliphatic Amines, aromatic amines, and / or amine adducts obtained by reaction of imidazoles with epoxy resins, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] Tertiary amines such as undecene-7, organic phosphines such as triphenylphosphine, dicyandiamide, etc. Can be mentioned. 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. These thermosetting agents may be used independently and 2 or more types may be used together.

The amount of the thermosetting agent is not particularly limited, but the preferred lower limit is 100 parts by weight of the silicone resin (when the bifunctional silicone resin is contained, the total of the silicone resin and the bifunctional silicone resin). 1 part by weight, the preferred upper limit is 200 parts by weight. Within this range, the thermosetting composition 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.

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

Although it does not specifically limit as a compounding quantity of the said hardening accelerator, The preferable minimum is 100 weight part of the said silicone resin (when the said bifunctional silicone resin is contained, the total of the said silicone resin and bifunctional silicone resin), 0.01 parts by weight, preferably 5 parts by weight. If it is less than 0.01 part by weight, the effect of adding the curing accelerator cannot be obtained, and if it exceeds 5 parts by weight, the coloration of the cured product, heat resistance, and light resistance are significantly reduced, which is not preferable. A more preferred lower limit is 0.05 parts by weight, and a more preferred upper limit is 1.5 parts by weight.

The thermosetting composition for optical semiconductors of the present invention preferably further contains fine particles having a metal element and / or a metalloid element. By containing the fine particles, the refractive index of the thermosetting composition for optical semiconductors of the present invention is increased, and light extraction of an optical semiconductor element such as an LED using the thermosetting composition for optical semiconductors of the present invention is performed. Excellent in properties.

A preferable upper limit of the average primary particle diameter of the fine particles is 20 nm. If it exceeds 20 nm, light scattering due to the fine particles may occur in the thermosetting composition for optical semiconductors of the present invention, and the thermosetting composition for optical semiconductors of the present invention may become cloudy. A more preferred lower limit is 3 nm, and a more preferred upper limit is 15 nm.

The fine particles have a metal element and / or a metalloid element.
The fine particles are preferably at least one selected from the group represented by 80% or more of the metal elements present in the fine particles. If it is less than 80%, the refractive index of the thermosetting composition for optical semiconductors of the present invention is not so high, and the light extraction property of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention is high. May be inferior.
Metal elements: Al, In, Ge, Sn, Ti, Zr, Hf

Further, in the fine particles, it is preferable that 80% or more of the semi-metal elements other than Si present in the fine particles are boron. If it is less than 80%, the refractive index of the thermosetting composition for optical semiconductors of the present invention is not so high, and the light extraction property of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention is high. May be inferior.

The fine particles are not particularly limited as long as the fine particles have the metal element and / or metalloid element. However, since the thermosetting composition for optical semiconductors of the present invention is excellent in improving the refractive index, zirconium is particularly preferable. It is preferable because the fine particles having an excellent refractive index and excellent light transmittance.

The blending amount of the fine particles is not particularly limited, but a preferable lower limit is 1 weight with respect to 100 parts by weight of the silicone resin (when the bifunctional silicone resin is contained, the total of the silicone resin and the bifunctional silicone resin). Parts, and the preferred upper limit is 100 parts by weight. When the amount is less than 1 part by weight, the refractive index of the thermosetting composition for optical semiconductors of the present invention may hardly be improved, and when it exceeds 100 parts by weight, it is difficult to adjust the viscosity. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 80 parts by weight.

The preferable lower limit of the refractive index of such fine particles is 1.50. If it is less than 1.50, the refractive index of the thermosetting composition for optical semiconductors of the present invention does not increase, and the light extraction property of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention is improved. It may be insufficient.
In addition, in this specification, the said refractive index is the value which measured the refractive index with respect to sodium D line | wire (589.3 nm) using the refractometer (Abbe type | formula) at the measurement temperature of 20 degreeC.

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

As a blending ratio of the coupling agent, a preferable lower limit is 0.1 weight with respect to 100 parts by weight of the silicone resin (when the bifunctional silicone resin is contained, the total of the silicone resin and the bifunctional silicone resin). Parts, and the preferred upper limit is 5 parts by weight. When the amount is less than 0.1 parts by weight, the effect of the coupling agent may not be sufficiently exhibited. When the amount exceeds 5 parts by weight, the excess coupling agent volatilizes, and the thermosetting composition for optical semiconductors of the present invention. When an object is cured, film loss may occur.

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

As a blending ratio of the antioxidant, a preferable lower limit is 0.001 weight with respect to 100 parts by weight of the silicone resin (when the bifunctional silicone resin is contained, the total of the silicone resin and the bifunctional silicone resin). Parts, and the preferred upper limit is 2 parts by weight. When the amount is less than 0.001 part by weight, the blending effect of the antioxidant may not be sufficiently exhibited. When the amount exceeds 2 parts by weight, the antioxidant volatilizes, and the thermosetting composition for optical semiconductors of the present invention. When a product is cured, film loss or the like may occur, or the cured product may become brittle.

The thermosetting composition for optical semiconductors of the present invention has additives such as an antifoaming agent, a colorant, a phosphor, a modifying agent, a leveling agent, a light diffusing agent, a thermally conductive filler, and a flame retardant as necessary. It may be blended.

Although it does not specifically limit as a viscosity of the thermosetting composition for optical semiconductors of this invention, A preferable minimum is 500 mPa * s and a preferable upper limit is 50,000 mPa * s. When it is less than 500 mPa · s, liquid dripping occurs when used as a sealing agent for an optical semiconductor element, and the light emitting element of the optical semiconductor element may not be sealed. When used as an element sealant, there is a problem of foaming, and the light emitting element of the optical semiconductor element may not be sealed uniformly and accurately. 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 thermosetting composition for optical semiconductors 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 thermosetting composition for optical semiconductors 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 thermosetting composition for optical semiconductors of this invention, and the transmittance | permeability of light with a wavelength of 400 nm made from Hitachi Ltd. "U-4000. It is the value measured using "."

Moreover, it is preferable that the decreasing rate of the light transmittance after a light resistance test is less than 10% in the thermosetting composition for optical semiconductors of this invention. If it is 10% or more, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. In addition, the light resistance test is a 100mW filter in which a filter that cuts light having a wavelength of 340nm or less is attached to a cured product having a thickness of 1mm obtained by curing the thermosetting composition for optical semiconductors of the present invention. 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 decreasing rate of the light transmittance after a heat resistance test is less than 10 in the thermosetting composition for optical semiconductors of this invention. If it is 10% or more, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors 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 thermosetting composition for optical semiconductors of the present invention is left in an oven at 150 ° C. for 500 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.

Since the thermosetting composition for optical semiconductors of the present invention contains silicon oxide fine particles surface-treated with the above-described silicone resin, thermosetting agent and organosilicon compound, the mechanical strength and transparency of the cured product are improved. In addition to being excellent, there is no discoloration due to heat generation or light emission of the light emitting element, excellent heat resistance and light resistance, and excellent adhesion to the housing material.

The method for producing the thermosetting composition for optical semiconductors 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 of the method include mixing the above-described fine powder silica, silicone resin, thermosetting agent, and, if necessary, predetermined amounts of a curing accelerator and an additive at room temperature or under heating.

Although it does not specifically limit as a use of the thermosetting composition for optical semiconductors of this invention, For example, optical semiconductor elements, such as a sealing agent, a housing material, die bond material for connecting to a lead electrode, a heat sink, etc., 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.
The sealing compound for optical semiconductors which uses the thermosetting composition for optical semiconductors of this invention is also one of this invention.
The die-bonding material for optical semiconductor elements which uses the thermosetting composition for optical semiconductors of this invention is also one of this invention.
The underfill material for optical semiconductor elements using the thermosetting composition for optical semiconductors of the present invention is also one aspect of the present invention.

(Die bond material for optical semiconductor elements)
Since the die-bonding material for optical semiconductor elements of the present invention is composed of the thermosetting composition for optical semiconductor elements of the present invention, it has excellent heat resistance, light resistance, and adhesiveness. In addition, since high transparency can be maintained under use conditions, light in the direction of the housing material of the optical semiconductor element is not absorbed and lost, which can contribute to the provision of an optical semiconductor element with high luminous efficiency. .

The die bond material for optical semiconductor elements of the present invention preferably further contains high thermal conductive fine particles. In the present specification, the high thermal conductive fine particles mean fine particles having high thermal conductivity.
By blending fine particles having high thermal conductivity, the die bond material for optical semiconductor elements of the present invention has excellent heat dissipation. For example, a heat sink is provided in a package of an optical semiconductor device, and the optical semiconductor is provided on the heat sink. It is preferable to fix the optical semiconductor by using a die bonding material for use because it is possible to greatly reduce thermal damage to the optical semiconductor.

As a thermal conductivity of the high thermal conductive fine particles to be blended in the die bond material for optical semiconductor elements of the present invention, a preferred lower limit is 60 kcal / m · hr · ° C. If the thermal conductivity is less than 60 kcal / m · hr · ° C., sufficient heat dissipation cannot be obtained without increasing the amount added, and viscosity adjustment may be difficult.

The high thermal conductive fine particles are not particularly limited. For example, metal particles such as nickel, tin, aluminum, gold, silver, copper, iron, cobalt, indium and alloys thereof; metal nitride such as boron nitride and aluminum nitride Product: Metal oxide such as aluminum oxide, magnesium oxide, titanium oxide, etc .; Carbon compound particles such as silicon carbide, graphite, diamond, amorphous carbon, carbon black, carbon fiber; Form other metal layer on resin particles and metal particles Metal coated particles and the like are raised.
As the metal-coated particles, for example, particles obtained by applying gold or silver plating to resin particles are preferable.

Moreover, when the particle | grains containing at least 1 type selected from the group which consists of gold | metal | money, silver, and copper are contained, the said die-bonding material will have high electroconductivity with heat conductivity, and is preferable. By using a die bond material having conductivity, when an optical semiconductor element having a structure in which electrode pads are provided on both upper and lower surfaces of the light emitting element, the lead electrode can be electrically connected with the die bond material, which is preferable.

Further, these fine particles having high thermal conductivity are preferably surface-treated so that they can be uniformly mixed at a high blending ratio.

The preferable lower limit of the amount of the high thermal conductive fine particles is 10% by weight, and the preferable upper limit is 95% by weight. If it is less than 10% by weight, sufficient thermal conductivity may not be obtained, and if it exceeds 95% by weight, viscosity adjustment may be difficult.

(Underfill material for optical semiconductor elements)
Since the underfill material for optical semiconductor elements of the present invention is formed using the thermosetting composition for optical semiconductors of the present invention, the original underfill material that relieves stress applied to electrode connection bumps in the case of flip chip mounting. While being suitable for the purpose, it is excellent in light resistance, heat resistance and adhesiveness, and can be suitably used. As described above, the underfill material for an optical semiconductor element of the present invention may be cured as an underfill material by performing flip chip mounting, and then the sealant may be cured, and the same sealant as the underfill material may be used. If used, they may be combined. The latter method is a more preferable production method because the tact time is shortened.

An optical semiconductor element using at least one of an encapsulant for optical semiconductor elements, a die bond material for optical semiconductor elements, and an underfill material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors of the present invention. Can be manufactured.

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 said light emitting element using the sealing compound for optical semiconductor elements of this invention, you may use another sealing agent together. In this case, after sealing the light emitting element with the sealant for optical semiconductor elements of the present invention, the periphery thereof may be sealed with the other sealant, and the light emitting element may be sealed with the other sealant. Then, the periphery thereof may be sealed with the optical semiconductor sealing agent of the present invention.
The other sealing agent is not particularly limited, and examples thereof include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass. 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 encapsulant for optical semiconductor elements of the present invention is not particularly limited. For example, the encapsulant for optical semiconductor elements of the present invention is pre-injected into a mold frame and light is emitted there. Examples include a method of immersing a lead frame or the like to which the element is fixed and then curing, a method of injecting the curing agent for an optical semiconductor element of the present invention into a mold having a light emitting element inserted therein, and the like.
Examples of the method for injecting the sealant for optical semiconductor elements of the present invention include injection by a dispenser, transfer molding, injection molding and the like. Furthermore, as another sealing method, the sealing agent for optical semiconductor elements of the present invention is dropped on the light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, and the light emitting element is formed at the bottom. The method etc. which inject | pour the sealing agent for optical semiconductor elements of this invention with a dispenser etc. to the arrange | positioned cup etc. and harden | cure.

Light formed by using the thermosetting composition for optical semiconductors of the present invention, the encapsulant for optical semiconductor elements of the present invention, the die bond material for optical semiconductor elements of the present invention and / or the underfill material for optical semiconductor elements of the present invention. A semiconductor element is also one aspect of the present invention.

1 and 2 are cross-sectional views schematically showing an example of an optical semiconductor element using the encapsulant for optical semiconductor elements and the die bonding material for optical semiconductor elements of the present invention, and FIG. It is sectional drawing which shows typically an example of the optical semiconductor element which uses the sealing agent for optical semiconductors, and the underfill material for optical semiconductor elements.

In the optical semiconductor element shown in FIG. 1, the light emitting element 11 is installed on the heat sink 16 via the die bonding material 10 for optical semiconductor elements of the present invention, and passes through the side surface from the upper surface of the light emitting element 11 and the housing material. Two lead electrodes 14 extended to the bottom surface are electrically connected by gold wires 13, respectively. And the light emitting element 11, the die-bonding material 10 for optical semiconductor elements of this invention, and the gold wire 13 are sealed with the sealing agent 12 for optical semiconductor elements of this invention.

FIG. 2 shows an optical semiconductor element in which the die bond material for an optical semiconductor element of the present invention has high conductivity by containing particles containing at least one selected from the group consisting of the above-mentioned gold, silver, and copper. Indicates.
In the optical semiconductor element shown in FIG. 2, the light emitting element 21 is installed via the die bonding material 20 for optical semiconductor elements of the present invention, and two leads extending from the upper surface of the housing material 25 through the side surface to the bottom surface. The end of one lead electrode 24 among the electrodes 24 is formed between the die bond material 20 for optical semiconductor elements of the present invention and the housing material 25, and the light emitting element is interposed via the die bond material 20 for optical semiconductor elements of the present invention. The other lead electrode 24 is electrically connected to the light emitting element 21 by a gold wire 23. And the light emitting element 21, the die-bonding material 20 for optical semiconductor elements of this invention, and the gold wire 23 are sealed with the sealing agent 22 for optical semiconductor elements of this invention.

In the optical semiconductor element of the present invention shown in FIG. 3, the light emitting element 31 is installed via the bump 33, and the optical semiconductor element underfill material 30 of the present invention is formed between the light emitting element 31 and the housing material 35. Has been. The two lead electrodes 34 extended from the upper surface of the housing material 35 to the bottom surface through the side surfaces are formed between the bumps 33 and the housing material 35 and are electrically connected to the light emitting element 31. ing. And the light emitting element 31 and the underfill material 30 for optical semiconductor elements of this invention are sealed with the sealing agent 32 for optical semiconductor elements of this invention.
In the optical semiconductor element of the present invention shown in FIG. 3, the underfill material 30 for the optical semiconductor element of the present invention is formed below the light emitting element 31 after connecting the light emitting element 31 and the lead electrode 34 with the bump 33. It is formed by filling the space from the lateral gap.

In the optical semiconductor element of the present invention, the housing material is not particularly limited, and examples thereof include conventionally known materials made of aluminum, polyphthalamide resin (PPA), polybutylene terephthalate resin (PBT), and the like. It is done.

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.

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting composition for optical semiconductors which is excellent in the mechanical strength of a hardened | cured material, transparency, heat resistance, and the adhesiveness with respect to the housing material etc. which enclose a semiconductor element, The sealing for optical semiconductor elements using the same A stop agent, a die bond material for an optical semiconductor element, and the thermosetting composition for an optical semiconductor, the sealant for an optical semiconductor, a die bond material for an optical semiconductor element, and / or an underfill material for an optical semiconductor element. An optical semiconductor element can be provided.

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 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. To the solution, potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) 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 = 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 B were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
Dimethyldimethoxysilane (400 g), methoxytrimethylsilane (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, 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 = 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 C were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 4)
In a separable flask equipped with a 2000 mL thermometer and a dropping device, dimethyldimethoxysilane (350 g), methoxytrimethylsilane (125 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (125 g) are added and stirred at 50 ° C. did. 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 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 = 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 D were determined in the same manner as in Synthesis Example 1.

(Example 1)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RX200 (fine powder silica [trimethylsilyl Treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 2)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RX200 (fine powder silica [trimethylsilyl Treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 3)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R974 (fine silica [dimethyl Silyl treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 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 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

Example 4
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R805 (fine powder silica [octyl) Silyl treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 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 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 5)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RA200H (fine powder silica [aminosilane Treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 6)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RY200 (fine powder silica [dimethyl Silicone treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 3 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 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 7)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R711 (fine silica [methacrylic] Silane treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 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 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 8)
Polymer C (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RX200 (fine powder silica [trimethylsilyl Treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

Example 9
Polymer D (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RX200 (fine powder silica [trimethylsilyl Treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 10)
Polymer B (70 g), Polymer A (30 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RX200 (fine powder silica [trimethylsilyl treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 11)
Polymer D (70 g), Polymer A (30 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL RX200 (fine powder silica [trimethylsilyl treatment, BET specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 g) was mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 1)
A sealing material for an optical semiconductor element was prepared in the same manner as in Example 1 except that fine powder silica was not used, and a cured product was obtained in the same manner as in Example 1 by using the obtained sealing agent for optical semiconductor element. Got.

(Comparative Example 2)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL 200 (fine powder silica [surface No treatment, specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 10 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 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

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

(Comparative Example 4)
VDT-431 (polysiloxane having a vinyl group, manufactured by Gelest, 45 g), HMS-031 (organohydrogenpolysiloxane, manufactured by Gelest, 55 g), octyl alcohol-modified solution of chloroplatinic acid (Pt concentration: 2% by weight, 0.05 g) was added and mixed and defoamed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled into a mold and cured at 100 ° C. for 3 hours and 150 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Evaluation)
The following evaluation was performed about the sealing agent for optical semiconductor elements obtained in Examples 1-11 and Comparative Examples 1-4. The results are shown in Tables 1 and 2.

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

(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 a light transmittance of 400 nm is measured using U-4000 manufactured by Hitachi, Ltd. went. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ When less than 10%: ○, When less than 10 to 40%: Δ, When 40 or more: x .

(Light transmittance after heat resistance test)
A cured product having a thickness of 1 mm was left in an oven at 150 ° C. for 500 hours, and a light transmittance of 400 nm was measured using U-4000 manufactured by Hitachi, Ltd. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ When less than 10%: ○, When less than 10 to 40%: Δ, When 40 or more: x .

(Adhesion test)
The sealants for optical semiconductor elements prepared in Examples and Comparative Examples were applied to aluminum, polyphthalamide resin (PPA), and polybutylene terephthalate resin (PBT), and 110 ° C. × 3 hours + 130 ° C. × 3 hours (implemented) Examples 1-9, Comparative Examples 1-2), 100 ° C. × 3 hours + 130 ° C. × 3 hours (Comparative Example 3) or 100 ° C. × 3 hours + 150 ° C. × 3 hours (Comparative Example 4) Then, in accordance with JIS K-5400, an adhesion test was performed using a cross-cut tape method with a clearance of 1 mm and 100 squares. In Table 1, when the number of peels was 0: ◯, when the number of peels 1 to 70: Δ, and when the number of peels 71 to 100: x.

(Hygroscopic reflow test, cooling cycle test)
(Preparation of die bond material for optical semiconductor elements)
A flaky silver powder (170 g) having an average particle size of 3 μm and a maximum particle size of 20 μm was added to polymer B (30 g), and the mixture was stirred and kneaded using three rolls.
The flaky silver powder-containing polymer (100 g) was added with Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 4.5 g), U-CAT SA 102 (San Apro, 0.075 g), AEROSIL RX200 (fine powder) Silica [trimethylsilyl treatment, specific surface area: 140 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 1.5 g) was added and mixed and degassed to obtain a die bond material for optical semiconductor elements.

A light emitting device having a main light emission peak of 460 nm was mounted on the housing material with lead electrode (PPA) using the produced die bonding material for an optical semiconductor device, and cured at 180 degrees for 15 minutes to fix the light emitting device. Subsequently, the light-emitting element and the lead electrode were electrically connected with a gold wire, and the sealant produced in the examples and comparative examples was injected, and 110 ° C. × 3 hours + 130 ° C. × 3 hours (Examples 1 to 11). Comparative Examples 1 and 2), 100 ° C. × 3 hours + 130 ° C. × 3 hours (Comparative Example 3) or 100 ° C. × 3 hours + 150 ° C. × 3 hours (Comparative Example 4), and light having a structure shown in FIG. A semiconductor element was produced.

The produced optical semiconductor elements (20 pieces) were left at 85 ° C. and 85 RH% for 24 hours, and the absorbed optical semiconductor elements were placed in a solder reflow oven (preheat 150 ° C. × 100 seconds + reflow [maximum temperature 260 ° C.]) three times. The number of cracks after passing and peeling from the housing material was confirmed (moisture absorption reflow test).
Furthermore, the optical semiconductor elements (20 pieces) subjected to the moisture absorption reflow test were subjected to 500 and 1000 cycles of cooling and heating at −40 ° C. for 30 minutes and 120 ° C. for 30 minutes to confirm the number of cracks and peeling from the housing material. (Cool cycle test).

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting composition for optical semiconductors which is excellent in the mechanical strength of a hardened | cured material, transparency, heat resistance, and the adhesiveness with respect to the housing material etc. which enclose a semiconductor element, The sealing for optical semiconductor elements using the same A stop agent, a die bond material for an optical semiconductor element, and the thermosetting composition for an optical semiconductor, the sealant for an optical semiconductor, a die bond material for an optical semiconductor element, and / or an underfill material for an optical semiconductor element. An optical semiconductor element can be provided.

It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing compound for optical semiconductors of this invention, and the die-bonding material for optical semiconductor elements. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing compound for optical semiconductors of this invention, and the die-bonding material for optical semiconductor elements. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing agent for optical semiconductors of this invention, and the underfill material for optical semiconductor elements. (A), (b) and (c) are states in which an alkyl group-containing silane compound having a structure represented by the general formulas (17), (18) and (19) is bonded to the surface of the silicon oxide fine particles. It is sectional drawing shown typically.

Explanation of symbols

10, 20 Die bond material for optical semiconductor element 11, 21, 31 Light emitting element 12, 22, 32 Sealant for optical semiconductor 13, 23 Gold wire 14, 24, 34 Lead electrode 15, 25, 35 Housing material 16 Heat sink 30 Underfill material for optical semiconductor 33 Bump 40 Silicon oxide fine particles 41, 42, 43 Organosilicon compounds

Claims (14)

It contains a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and silicon oxide fine particles surface-treated with an organosilicon compound. Thermosetting composition for optical semiconductors. ^{2. The} thermosetting composition for optical semiconductors according to claim 1, wherein the silicon oxide fine particles surface-treated with the organosilicon compound have a BET specific surface area of 30 to 400 m ² / g. 3. The optical semiconductor heat according to claim 1, wherein the organosilicon compound is an alkyl group-containing silane compound having a structure represented by the following general formula (17), (18) or (19): Curable composition.

In general formulas (17) and (18), R represents an alkyl group having 1 to 3 carbon atoms, and in general formula (19), R ′ represents an alkyl group having 4 to 8 carbon atoms. The thermosetting composition for optical semiconductors according to claim 1, wherein the organosilicon compound is a compound having a dimethylsilyl group or a trimethylsilyl group. The silicone resin having one or more cyclic ether-containing groups in the molecule is mainly composed of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). When the total number of units is 1, the content of the structural unit represented by the general formula (1) is 0.6 to 0.95 (in terms of mole), and the structural unit represented by the general formula (2) The content of the structural unit is 0.05 to 0.4 (molar conversion), and the content of the cyclic ether-containing group is 5 to 40 mol%. Or the thermosetting composition for optical semiconductors of 4.

In the general formula (1) and ^(2), R 1, ^{R 2} and ^{R 3} is at least one represents a cyclic ether-containing group, ^R 1, ^{R 2} and ^{R 3} other than the cyclic ether-containing group, the carbon Represents a hydrocarbon of formula 1 to 8 or a fluorinated product thereof, which may be the same or different from each other, and furthermore, in the repeating structure in the silicone resin skeleton, a plurality of different types of R ¹ , R ² and R ³ may be contained. Furthermore, the thermosetting for optical semiconductors of Claim 1, 2, 3, 4 or 5 characterized by containing bifunctional silicone resin with an average compositional formula represented by the following general formula (15) or (16) Sex composition.

In the general formula (15), r satisfies r / (r + s) = 0.6 to 0.95, s / (r + s) = 0.05 to 0.4, and R ³⁹ and / or R ⁴⁰ are cyclic It is an ether-containing group, and R ³⁷ and R ³⁸ each represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different. When only one of R ^{39 and} R ⁴⁰ is a cyclic ether-containing group, the other represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the general formula (16), t, u, and v satisfy t + u / (t + u + v) = 0.6 to 0.95, v / (t + u + v) = 0.05 to 0.4, and R ⁴⁵ and / or R ⁴⁶ is a cyclic ether-containing group, and R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as or different from each other. It may be. Further, when only one of R ^{45 and} R ⁴⁶ is a cyclic ether-containing group, the other represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and (R ⁴¹ R ⁴² SiO _2/2 ) and (R ⁴³ R ⁴⁴ SiO _2/2 ) is different in structure. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, or 6, wherein the silicone resin contains 0.5 to 10 mol% of an alkoxy group. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the cyclic ether-containing group is a glycidyl group and / or an epoxycyclohexyl group. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the thermosetting agent is an acid anhydride. An encapsulant for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. A die-bonding material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. The die bond material for an optical semiconductor according to claim 11, further comprising high thermal conductive fine particles. An underfill material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7, 8, or 9, the sealant for optical semiconductor elements according to claim 10, and the sealing agent according to claim 11 or 12. A die-bonding material for optical semiconductor elements and / or an underfill material for optical semiconductor elements according to claim 13 is used.

Images