JP2008174640A - Thermosetting composition for photo-semiconductor, die-bonding material for photo-semiconductor element, underfill material for photo-semiconductor element, sealant for photo-semiconductor element and photo-semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for a photo-semiconductor, having a high penetrating property, excellent in close adhesion to a housing material, etc., for sealing a light-emitting element and light fastness against a short wave length light on using it as a sealant for sealing the light-emitting element of a photo-semiconductor element such as a light-emitting diode, etc., and further, since having an extremely high heat resistance, without developing discoloration caused by the heat generation of the light-emitting element sealed by the cured material. <P>SOLUTION: The thermosetting composition for the photo-semiconductor, containing a silicone resin having ≥1 cyclic ether-containing group in its molecule, a liquid state acid anhydride and a curing accelerator is provided. Either of the pseudo light extinction coefficients of the liquid state acid anhydride and curing accelerator at 25°C in tetrahydrofuran (THF) in 400 nm wave length is ≤0.1, and also the pseudo light extinction coefficient of the mixture of the liquid state acid anhydride and curing accelerator at 25°C in 400 nm wave length is 0.2 to 10. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention is highly transmissive and, when used as a sealing agent for sealing a light emitting element of an optical semiconductor element such as a light emitting diode, has an adhesiveness to a housing material that encloses the light emitting element, and has a short wavelength. Since it has excellent light resistance to light and has extremely high heat resistance, it does not cause discoloration due to heat generation of the light-emitting element sealed in the cured product, and for optical semiconductor elements. Sealant, die bond material for optical semiconductor element, underfill material for optical semiconductor element, thermosetting composition for optical semiconductor, sealant for optical semiconductor element, die bond material for optical semiconductor element and / or for optical semiconductor element The present invention relates to an optical semiconductor element using an underfill material.

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, such a conventional sealant using a silicone resin has excellent heat resistance and light resistance, but has problems such as low adhesion and low tendency to peel, and excellent heat resistance and light resistance. There has been a strong demand for a highly reliable sealant having high adhesion.
JP 2003-277473 A JP 2002-314142 A

In view of the above situation, the present invention is highly permeable and, when used as a sealing agent for sealing a light emitting element of an optical semiconductor element such as a light emitting diode, adherence to a housing material or the like enclosing the light emitting element, And since it has excellent light resistance to light of short wavelengths and has extremely high heat resistance, the thermosetting composition for optical semiconductors does not cause discoloration due to heat generation of the light emitting element sealed in the cured product. , Optical semiconductor element encapsulant, optical semiconductor element die bond material, optical semiconductor element underfill material, optical semiconductor thermosetting composition, optical semiconductor element encapsulant, optical semiconductor element die bond material, and / or Alternatively, an object is to provide an optical semiconductor element using an underfill material for an optical semiconductor element.

The present invention is a thermosetting composition for optical semiconductors containing a silicone resin having one or more cyclic ether-containing groups in the molecule, a liquid acid anhydride and a curing accelerator,
The liquid acid anhydride is represented by the following formula (1), the pseudo-absorption coefficient (ε1) at a wavelength of 400 nm in tetrahydrofuran (THF) at 25 ° C., and the curing accelerator represented by the following formula (2). The pseudo-absorption coefficient (ε2) at a wavelength of 400 nm in tetrahydrofuran (THF) at 25 ° C. is 0.1 or less, and the following formula (3) of the mixture of the liquid acid anhydride and the curing accelerator: ), A thermosetting composition for optical semiconductors having a pseudo-absorption coefficient (ε ′) of 0.2 to 10 at 25 ° C. and a wavelength of 400 nm.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention have no absorption of light having a wavelength of 400 nm by themselves with a silicone resin having one or more cyclic ether-containing groups in the molecule. A sealant containing a liquid acid anhydride and a curing accelerator exhibiting a specific light absorption characteristic that causes absorption is highly permeable to light of a short wavelength in the blue to ultraviolet region, and is used for an optical semiconductor element such as a light emitting diode. When used as a sealant for sealing a light-emitting element, it has excellent adhesion to a housing material that encloses the light-emitting element, light resistance to short-wavelength light, and extremely high heat resistance. Thus, the present inventors have found that no discoloration occurs due to heat generation of the light emitting element sealed, and thus completed the present invention.

The thermosetting composition for optical semiconductors of the present invention contains a liquid acid anhydride and a curing accelerator.
The liquid acid anhydride and the curing accelerator are the upper limits of the pseudo-absorption coefficient (ε1) and (ε2) at a wavelength of 400 nm in tetrahydrofuran (THF) represented by the above formulas (1) and (2), respectively. Is 0.1, and the lower limit of the pseudo-absorption coefficient (ε ′) at 25 ° C. and a wavelength of 400 nm represented by the above formula (3) of the mixture of the liquid acid anhydride and the curing accelerator is 0.00. 2. The upper limit is 10.
Here, the pseudo-absorption coefficient (ε1) and (ε2) of the liquid acid anhydride or the curing accelerator are each independently about the liquid acid anhydride or the curing accelerator at 25 ° C. and a wavelength of 400 nm in THF. The extinction coefficient is a value calculated based on the above formula (1) or (2). On the other hand, the extinction coefficient of the mixture of the liquid acid anhydride and the curing accelerator needs to be calculated using the concentration of the complex formed later by the liquid acid anhydride and the curing accelerator in the mixture. Since it is virtually impossible to directly measure the complex concentration in the mixture, in this specification, using the concentration of the curing accelerator in the mixture, the extinction coefficient at 25 ° C. and the wavelength of 400 nm is expressed by the above formula. The value calculated based on (3) was regarded as the number of extinction systems of the above mixture, and this was defined as the pseudo extinction coefficient (ε ′). In this specification, “liquid acid anhydride” means an acid anhydride that is liquid at room temperature.

Liquid anhydrides and curing accelerators having such pseudo extinction coefficients (ε1), (ε2), and (ε ′) are almost free from light having a wavelength of around 400 nm, respectively, as shown in FIGS. Although it does not show absorption, when it is a mixture of the liquid acid anhydride and the curing accelerator, it means that it has absorption with respect to light having a wavelength of around 400 nm. FIG. 4 shows a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)) as the liquid acid anhydride, and tricyclohexylphosphine as the curing accelerator. FIG. 5 is a graph showing the relationship between the pseudo-absorption coefficient (ε1), (ε2) and the pseudo-absorption coefficient (ε ′) of the mixture and the irradiation light wavelength, and FIG. 5 shows the pseudo-absorption coefficient (ε1) of FIG. , (Ε2) and an enlarged graph of the relationship between the irradiation light wavelength.

The thermosetting composition for optical semiconductors of the present invention contains a liquid acid anhydride satisfying such pseudo extinction coefficients (ε1), (ε2), and (ε ′) and a curing accelerator. Has excellent heat resistance (coloring resistance), can maintain excellent transparency even under thermal conditions, and can be suitably used particularly for a semiconductor encapsulant. The reason for this is not particularly clear, but it is considered that the curing reaction mechanism of the thermosetting composition for optical semiconductors of the present invention is as follows.
That is, in the thermosetting composition for optical semiconductors of the present invention, it is considered that a complex is formed by a strong interaction between the liquid acid anhydride and the curing accelerator. When the thermosetting composition for optical semiconductors of the present invention is cured, this complex reacts with an epoxy group in a silicone resin described later to form an ester bond. Since this ester bond has a structure excellent in heat resistance, the cured product of the thermosetting composition for optical semiconductors of the present invention is considered to be extremely excellent in heat resistance. In contrast, a sealing agent containing a conventional silicone resin having an epoxy group and a curing accelerator does not form the above-described complex, and when cured, the epoxy group in the silicone resin and the curing accelerator React to form an ether bond such as “CH ₂ —O—CH” having “CH ₂ ” and “CH” at both ends. Since such an ether bond is easily deteriorated by heat as compared with the ester bond, it is considered that the cured product of the conventional sealant has insufficient heat resistance.

The liquid acid anhydride and the curing accelerator forming the complex are represented by the above formulas (1) and (2), respectively, and the pseudo absorption coefficient (ε1) of light having a wavelength of 400 nm in THF at 25 ° C., The upper limit of (ε2) is 0.1. This indicates that the liquid acid anhydride and the curing accelerator alone hardly absorb light having a wavelength of 400 nm. When it exceeds 0.1, coloring will be seen by the hardened | cured material immediately after hardening of the thermosetting composition for optical semiconductors of this invention, and it will become impossible to use for optical semiconductor element sealing agent use.

The lower limit of the pseudo-absorption coefficient (ε ′) represented by the above formula (3) at a wavelength of 400 nm of the mixture of the liquid acid anhydride and the curing accelerator is 0.2 and the upper limit is 10. This indicates that the complex formed by mixing the liquid acid anhydride and the curing accelerator described above absorbs light having a wavelength of 400 nm. If the complex is less than 0.2, the complex formation is performed. However, the effect of improving the heat resistance by suppressing the ether bond due to the change of the reaction mechanism cannot be sufficiently obtained. When it exceeds 10, coloring will be seen by the hardened | cured material immediately after hardening of the thermosetting composition for optical semiconductors of this invention, and it will become impossible to use for optical semiconductor element sealing agent use. The preferable lower limit of (ε ′) is 0.4, and the preferable upper limit is 5.

As the liquid acid anhydride and the curing accelerator, the above-described complex can be formed, and the pseudo-absorption coefficient (ε1) and (ε2) described above each independently and the pseudo-absorption coefficient (ε ′) described above by the mixture. It is necessary to select a combination that can be achieved. In selecting such a liquid acid anhydride and a curing accelerator, the compound is a combination of a donor and an acceptor, and the donor's HOMO (High Occupied Molecular Orbital) and the acceptor's LUMO (Lowest It is preferable to select one having an energy level close to that of Unoccupied Molecular Orbital.
As such a liquid acid anhydride, for example, an acid anhydride having a cyclic hydrocarbon skeleton is preferably used. Specifically, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hydrogenated methylnadic anhydride Products, cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, etc., among others, hexahydrophthalic anhydride, methylhexa At least one selected from the group consisting of hydrophthalic anhydride and hydrogenated methyl nadic anhydride is preferably used. The liquid acid anhydride may be a mixture of two or more kinds, and may be a solid and liquid mixture as long as it has liquid properties after mixing.

Further, as the curing accelerator, it is preferable to appropriately select the curing accelerator such that the combination with the liquid acid anhydride has the above-described relationship. Among them, the liquid acid anhydride is hexahydrophthalic anhydride, methylhexahexan. In the case of at least one selected from the group consisting of hydrophthalic anhydride and hydrogenated methyl nadic anhydride, a compound having a structure represented by the following general formula (1) is preferably used.

In general formula (1), R ′, R ″, and R ′ ″ may be different or the same, and may have a branched or cyclic alkyl group having 1 to 12 carbon atoms. Represents.
Among these curing accelerators, tricycloalkylphosphine is preferably used.

Although it does not specifically limit as a compounding quantity of the hardening accelerator with respect to the said liquid acid anhydride, From a viewpoint of forming the complex mentioned above effectively, the preferable minimum of the said hardening accelerator with respect to 100 weight part of the said liquid acid anhydride. Is 0.01 part by weight, and the preferred upper limit is 2 parts by weight. When the amount is less than 0.01 parts by weight, the above-described complex may not be formed suitably. When the amount exceeds 2 parts by weight, the heat resistance of the thermosetting composition for optical semiconductors of the present invention is reduced.

Further, the blending amount of the liquid acid anhydride in the thermosetting composition for optical semiconductors of the present invention is not particularly limited, but the preferred lower limit is 1 part by weight and the preferred upper limit is 100 parts by weight of the silicone resin described later. 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 of the cured product, and has a sufficiently low moisture permeability. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 120 parts by weight.

The thermosetting composition for optical semiconductors of the present invention contains a silicone resin having one or more cyclic ether-containing groups in the molecule.
In the thermosetting composition for optical semiconductors of the present invention, the silicone resin contains a resin component whose average composition formula is represented by the following general formula (2).

When the silicone resin contains a resin component having an average composition formula represented by the general formula (2), the thermosetting composition for an optical semiconductor according to the present invention is suitable for light having a short wavelength in a blue to ultraviolet region. Light-emitting element for optical semiconductor elements such as light-emitting diodes, which has high transparency and is excellent in heat resistance and light resistance without causing heat generation or discoloration due to light emission of the light-emitting element to be sealed when used as a sealing agent for optical semiconductor elements. When this is sealed, the optical semiconductor element has excellent adhesion to the housing material or the like.
In addition, the said average composition formula is represented with the said Formula (2) not only when the thermosetting composition for optical semiconductors of this invention contains only the resin component represented by the said Formula (2). In the case of a mixture containing resin components having various structures, the average of the composition of the resin components contained also means the case represented by the above formula (2).

In the general formula (2), at least one of R ^{1 to} R ⁶ represents a cyclic ether-containing group.
The cyclic ether-containing group is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Of these, a glycidyl group and / or an epoxycyclohexyl group are preferable.

The glycidyl group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl Group, 4-glycidoxybutyl group and the like.

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

In the silicone resin having an average composition formula represented by the general formula (2), the preferable lower limit of the content of the cyclic ether-containing group is 0.1 mol%, and the preferable upper limit is 50 mol%. When the content is less than 0.1 mol%, the reactivity between the silicone resin and the complex formed from the liquid acid anhydride and the curing accelerator described above is significantly reduced, and the thermosetting composition for optical semiconductors of the present invention is reduced. Curability may be insufficient. If it exceeds 50 mol%, the number of cyclic ether-containing groups not involved in the reaction between the silicone resin and the complex formed from the liquid acid anhydride and the curing accelerator described above increases, and the thermosetting composition for optical semiconductors of the present invention The heat resistance of may decrease. A more preferred lower limit is 5 mol%, and a more preferred 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 silicone resin represented by the general formula (2), R ^{1 to} R ⁶ other than the cyclic ether-containing group represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

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

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

In the silicone resin represented by the general formula (2), the structural unit represented by (R ⁶ SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following general formula (2-3) Or a structure represented by (2-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxyl group or an alkoxy group, or silicon in a trifunctional structural unit It includes a structure in which one of oxygen atoms bonded to an atom constitutes a hydroxyl group or an alkoxy group.
(R ⁶ SiX ₂ O _1/2 ) (2-3)
(R ⁶ SiXO _2/2 ) (2-4)
In the general formulas (2-3) and (2-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the silicone resin represented by the general formula (2), the structural unit represented by (SiO _4/2 ) (hereinafter also referred to as tetrafunctional structural unit) is represented by the following general formula (2-5), ( 2-6) or (2-7), that is, a structure in which three or two oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit constitute a hydroxyl group or an alkoxy group, or four It includes a structure in which one of oxygen atoms bonded to a silicon atom in the functional structural unit constitutes a hydroxyl group or an alkoxy group.
(SiX ₃ O _1/2 ) (2-5)
(SiX ₂ O _2/2 ) (2-6)
(SiXO _3/2 ) (2-7)
In the general formulas (2-5), (2-6), and (2-7), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. To express.

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

In the general formula (2), a is a numerical value that satisfies the relationship that the lower limit of a / (a + b + c + d) is 0 and the upper limit is 0.2. If it exceeds 0.2, the heat resistance of the thermosetting composition for optical semiconductors of the present invention may deteriorate.

In the general formula (2), b is a numerical value that satisfies the relationship that the lower limit of b / (a + b + c + d) is 0.3 and the upper limit is 1.0. If it is less than 0.3, the cured product of the thermosetting composition for optical semiconductors of the present invention becomes too hard, and when used as a semiconductor peripheral member such as a sealant, die bonding material, underfill, etc. Cracks or the like may occur between the adherends.

In the general formula (2), c is a numerical value that satisfies the relationship that the lower limit of c / (a + b + c + d) is 0 and the upper limit is 0.5. If it exceeds 0.5, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention.

Furthermore, in the general formula (2), d is a numerical value that satisfies the relationship that the lower limit of d / (a + b + c + d) is 0 and the upper limit is 0.3. If it exceeds 0.3, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention.

When the 29Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed on the silicone resin represented by the general formula (2) on the basis of tetramethylsilane (hereinafter referred to as TMS), a slight variation is observed depending on the type of the substituent. However, the peak corresponding to the structural unit represented by (R ¹ R ² R ³ SiO _1/2 ) _a in the general formula (2) appears in the vicinity of +10 to 0 ppm, and (R) in the general formula (2) ⁴ R ⁵ SiO _2/2 ) Each peak corresponding to the bifunctional structural unit of ( _b ) and (2-2) appears in the vicinity of −10 to −30 ppm, and (R ⁶ SiO _3/2 ) of the above general formula (2) _c , peaks corresponding to the trifunctional structural units of (2-3) and (2-4) appear in the vicinity of −50 to −70 ppm, and (SiO _4/2 ) _d of the general formula (2), (2 -5), tetrafunctional structures of (2-6) and (2-7) Each peak corresponding to the position appears in the vicinity of -90~-120ppm.
Therefore, it is possible to measure the ratio of the general formula (2) by measuring 29Si-NMR and comparing the peak areas of the respective signals.
However, when the 29Si-NMR measurement based on the TMS cannot be distinguished from the functional structural unit of the general formula (2), not only the 29Si-NMR measurement result but also 1H-NMR or 19F-NMR The ratio of the structural units can be discriminated by using the results measured by the above as necessary.

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

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

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

Specific examples of the resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule of the silicone resin include the following general formulas (3) to ( The resin represented by 6) can be used.

上記一般式（３）において、Ｒ^１２は、環状エーテル含有基であり、Ｒ^１０、Ｒ^１１は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。ｅ／（ｅ＋ｆ）は、上記条件（１）を満し、ｆ／（ｅ＋ｆ）は上記条件（２）を満たす。

In the general formula (3), R ¹² is a cyclic ether-containing group, R ¹⁰ and R ¹¹ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. e / (e + f) satisfies the above condition (1), and f / (e + f) satisfies the above condition (2).

上記一般式（４）において、Ｒ^１４及び／又はＲ^１５は、環状エーテル含有基であり、Ｒ^１３は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表す。また、Ｒ^１４又はＲ^１５のいずれか一方のみが環状エーテルである場合、他方は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表す。ｇ／（ｇ＋ｈ）は上記条件（１）を満たし、ｈ／（ｇ＋ｈ）は上記条件（２）を満たす。

In the general formula (4), R ¹⁴ and / or R ¹⁵ is a cyclic ether-containing group, and R ¹³ represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. When only one of R ^{14 and} R ¹⁵ is a cyclic ether, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. g / (g + h) satisfies the above condition (1), and h / (g + h) satisfies the above condition (2).

上記一般式（５）において、Ｒ^１８及び／又はＲ^１９は、環状エーテル含有基であり、Ｒ^１６、Ｒ^１７、Ｒ^２０は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。また、Ｒ^１８又はＲ^１９のいずれか一方のみが環状エーテルである場合、他方は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表す。（ｉ＋ｊ）／（ｉ＋ｊ＋ｋ）は上記条件（１）を満たし、ｋ／（ｉ＋ｊ＋ｋ）は上記条件（２）を満たす。

In the general formula (5), R ¹⁸ and / or R ¹⁹ is a cyclic ether-containing group, and R ¹⁶ , R ¹⁷ , and R ²⁰ are linear or branched hydrocarbons having 1 to 8 carbon atoms or It represents the fluorinated product, and these may be the same or different from each other. When only one of R ^{18 and} R ¹⁹ is a cyclic ether, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. (I + j) / (i + j + k) satisfies the above condition (1), and k / (i + j + k) satisfies the above condition (2).

上記一般式（６）において、Ｒ^２３は、環状エーテル含有基であり、Ｒ^２１、Ｒ^２２、Ｒ^２４は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。ｌ／（ｌ＋ｍ＋ｎ）は上記条件（１）を満たし、（ｍ＋ｎ）／（ｌ＋ｍ＋ｎ）は上記条件（２）を満たす。

In the general formula (6), R ²³ is a cyclic ether-containing group, and R ²¹ , R ²² , and R ²⁴ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. l / (l + m + n) satisfies the condition (1), and (m + n) / (l + m + n) satisfies the condition (2).

Especially, it is preferable to contain the resin component represented by the said General formula (3) or (6). Moreover, in said general formula (3)-(6), it is preferable that cyclic ether containing group contains either one of a glycidyl group or an epoxy cyclohexyl group.

It is preferable that the said silicone resin contains 0.5-10 mol% of alkoxy groups. By containing such an alkoxy group, heat resistance and light resistance are drastically improved. This is presumably because the curing rate can be drastically improved by containing an alkoxy group in the silicone resin, thereby preventing thermal degradation during curing.

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.

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

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

The silicone resin preferably does not contain a silanol group. The silanol group is not preferable because the storage stability of the polymer is remarkably deteriorated and the storage stability when the resin composition is obtained is also remarkably deteriorated. Such silanol groups can be reduced by heating in a 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 method of introducing a substituent by a hydrosilylation reaction between a silicone resin having a SiH group and a vinyl compound having a cyclic ether group, (2) Examples thereof include a method in which a siloxane compound and a siloxane 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.

As the silicone resin having the SiH group, after reacting the vinyl compound having a SiH group in the molecule and the cyclic ether-containing group, the structure represented by the general formula (2) described above, preferably What has the structure represented by any of the above general formulas (3) to (6) may be used.

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 glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate And epoxy group-containing compounds such as vinylcyclohexene oxide.

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 method (2), examples of the siloxane compound include alkoxysilanes having a siloxane unit represented by the following general formulas (7), (8), (9), and (10), or partial hydrolysates thereof.

R ²⁵ R ²⁶ R ²⁷ Si (OR) (7)
R ²⁸ R ²⁹ Si (OR) ₂ (8)
R ³⁰ Si (OR) ₃ (9)
Si (OR) ₄ (10)

In the general formulas (7) to (10), R ^{25 to} R ³⁰ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR is linear or branched. Represents an alkoxy group having 1 to 4 carbon atoms.

In the general formulas (7) to (10), when R ^{25 to} R ³⁰ are linear or branched hydrocarbons having 1 to 8 carbon atoms, specifically, 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 Group, t-pentyl group, isohexyl group and the like.

In the general formulas (7) to (10), 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.

In the above siloxane compound, the compounding ratio of the alkoxysilane having a siloxane unit represented by the general formulas (7) to (10) or a partial hydrolyzate thereof is subjected to a condensation reaction with a siloxane compound having a cyclic ether-containing group described later. The silicone resin synthesized in this way is appropriately adjusted so as to have a structure represented by the above general formula (2), preferably a structure represented by any one of the above general formulas (3) to (6).

Examples of the siloxane compound having a cyclic ether-containing group include alkoxysilane having a cyclic ether-containing group represented by the following general formula (11) or a partial hydrolyzate thereof.

R ³¹ R ³² _d Si (OR ³³ ) _(3-d) (11)

In the general formula (11), R ³¹ is a cyclic ether-containing group, R ³² represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and R ³³ is linear. Alternatively, it represents a branched alkyl group having 1 to 4 carbon atoms, and d is 0 or 1.

In the general formula (11), the cyclic ether-containing group represented by R ³¹ is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Of these, a glycidyl group and / or an epoxycyclohexyl group are preferable.

The glycidyl group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl Group, 4-glycidoxybutyl group and the like.

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

In the general formula (11), R ³² represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and as the linear or branched hydrocarbon having 1 to 8 carbon atoms, It is not particularly limited, and examples thereof include the same as those described in the general formula (2). In the general formula (11), d is 0 or 1, and when d is 0, the siloxane compound having a cyclic ether-containing group is a trialkoxysilane having a cyclic ether-containing group or a partial hydrolyzate thereof. When d is 1, the siloxane compound having a cyclic ether-containing group is a dialkoxysilane having a cyclic ether-containing group or a partial hydrolyzate thereof.

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

Specific examples of the organodialkoxysilane having a cyclic ether-containing group include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidide. Examples include xylpropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, and 2,3-epoxypropyl (methyl) dimethoxysilane.

In the method (2), as a specific method for the condensation reaction of the siloxane compound and the siloxane compound having a cyclic ether-containing group, for example, the siloxane compound and the compound having a cyclic ether group are mixed with water and an acid. Or the method of making it react in presence of a basic catalyst and synthesize | combining a silicone resin is mentioned.
The siloxane compound may be reacted in advance in the presence of water and an acid or basic catalyst, and then the siloxane compound having a cyclic ether group may be reacted.

In the method (2), when the siloxane compound and the compound having a cyclic ether-containing group are reacted in the presence of water and an acid or a basic catalyst, the compound having the cyclic ether-containing group is It mix | blends so that a lower limit may be 0.1 mol% and an upper limit may be 50 mol% with respect to all the organic groups couple | bonded with the silicon atom of the said siloxane compound and the compound which has a cyclic ether containing group.

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

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

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

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

In the condensation reaction between the siloxane compound and the siloxane compound having a cyclic ether-containing group, the silicone resin to be synthesized can be prevented from precipitating from the reaction system, and the water and free water due to the condensation reaction can be removed azeotropically. Therefore, it is preferable to use an organic solvent.
Examples of the organic solvent include aromatic organic solvents such as toluene and xylene; ketone organic solvents such as acetone and methyl isobutyl ketone; aliphatic organic solvents such as hexane, heptane and octane. Of these, aromatic organic solvents are preferably used.

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

From the viewpoint of adjusting the amount of alkoxy groups, it is preferable to synthesize a silicone resin by the above method (2).
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. Moreover, you may adjust the quantity of an alkoxy group by making it condense with a compound like the said General formula (7).

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 part by weight and a preferable upper limit is 100 parts by weight with respect to 100 parts by weight of the silicone resin. 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 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the silicone resin. 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 part by weight and a preferable upper limit is 2 parts by weight with respect to 100 parts by weight of the silicone resin. 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.

Moreover, the thermosetting composition for optical semiconductors of the present invention may contain silica fine powder, high molecular weight silicone resin, and the like in order to adjust the viscosity. In particular, the silica fine powder not only has a thickening action but also acts as a thixotropic agent, so that the fluidity control of the thermosetting composition for optical semiconductors of the present invention and the prevention effects such as sedimentation of the phosphor also occur. Therefore, it is more preferable.

Although it does not specifically limit as an average particle diameter of the said silica fine powder, A preferable upper limit is 100 nm. If it exceeds 100 nm, the transparency of the thermosetting composition for optical semiconductors of the present invention may decrease.

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

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

The 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. If it is less than 500 mPa · s, liquid dripping may occur when used as a sealing agent for an optical semiconductor element, and the optical semiconductor element may not be sealed. The semiconductor element may not be sealed. A more preferred lower limit is 1000 mPa · s, and a more preferred upper limit is 10,000 mPa · s.
In addition, in this specification, the said viscosity is the value measured on 25 degreeC and 5 rpm conditions using the E-type viscosity meter (the Toki Sangyo company make, TV-22 type | mold).

The 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.

The thermosetting composition for optical semiconductors of the present invention satisfies the silicone resin having one or more cyclic ether-containing groups in the molecule and the above-described pseudo-absorption coefficients (ε1), (ε2), and (ε ′). Because it contains a liquid acid anhydride and a curing accelerator, it is highly permeable to light with a short wavelength in the blue to ultraviolet region, and is used as a sealing agent for sealing light emitting elements of optical semiconductor elements such as light emitting diodes. In addition, it has excellent adhesion to a housing material or the like that encloses the light emitting element, and further has extremely high heat resistance, so that discoloration due to heat generation of the sealed light emitting element does not occur.

The method for producing the thermosetting composition for optical semiconductors of the present invention is not particularly limited. Examples include a method of mixing predetermined amounts of the above-described silicone resin, liquid acid anhydride, fine particles, curing accelerator, additive, and the like 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 preferable 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.
Furthermore, the encapsulant for optical semiconductor elements of the present invention can also be used as a die bond material for fixing the light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.

The thermosetting composition for optical semiconductors of the present invention satisfies the silicone resin having one or more cyclic ether-containing groups in the molecule and the above-described pseudo-absorption coefficients (ε1), (ε2), and (ε ′). Because it contains a liquid acid anhydride and a curing accelerator, it is highly permeable to light with a short wavelength in the blue to ultraviolet region, and is used as a sealing agent for sealing light emitting elements of optical semiconductor elements such as light emitting diodes. In addition, it has excellent adhesion to a housing material or the like that encloses the light emitting element, and further has extremely high heat resistance, so that discoloration due to heat generation of the sealed light emitting element does not occur.
The housing material is not particularly limited, and examples thereof include conventionally known materials made of aluminum, polyphthalamide resin (PPA), polybutylene terephthalate resin (PBT), or the like.

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.

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

According to the present invention, when used as a sealant that seals a light-emitting element of an optical semiconductor element such as a light-emitting diode, according to the present invention, adhesion to a housing material or the like enclosing the light-emitting element, and a short wavelength The thermosetting composition for optical semiconductors and the optical semiconductor elements, which are excellent in light resistance to light and have extremely high heat resistance, and do not cause discoloration due to heat generation of the light emitting elements sealed in the cured product. Sealant for optical semiconductor, die bond material for optical semiconductor element, underfill material for optical semiconductor element, thermosetting composition for optical semiconductor, sealant for optical semiconductor element, die bond material for optical semiconductor element and / or optical semiconductor element An optical semiconductor element using the underfill material 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, Mw = 25000, and (Me ₂ SiO _2/2 ) _0.90 (EpMeSiO _2/2 ) _0.10 from 29Si-NMR.
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 29Si-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)
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 C. The molecular weight of the polymer C is Mn = 2900, Mw = 4600, and (Me ₂ SiO _2/2 ) _0.65 (MeSiO _3/2 ) _0.22 (EpSiO _3/2 ) _0.13 from 29Si-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 C were determined in the same manner as in Synthesis Example 1.

(Example 1)
Rikacid MH-700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd., 25 g), tricyclohexylphosphine (curing accelerator, 0.2 g) And dissolved by heating. Polymer A (100 g) was added to the solution 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 2)
Ricacid MH-700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), manufactured by Shin Nippon Rika Co., Ltd., 30 g), distilled and purified tributylphosphine (curing accelerator, 0 0.2 g) and polymer A (100 g) were added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 3)
Rikacid MH-700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd., 25 g), tricyclohexylphosphine (curing accelerator, 0.2 g) And dissolved by heating. Polymer B (100 g) was added to the solution 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
Rikacid MH-700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd., 25 g), tricyclohexylphosphine (curing accelerator, 0.2 g) And dissolved by heating. Polymer C (100 g) was added to the solution 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 1)
Rikacid MH-700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd., 25 g), distilled and purified dimethylcyclohexylamine (curing accelerator, 0 0.1 g) and polymer A (100 g) were added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 2)
Rikacid MH-700G (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd., 25 g), triphenylphosphine (curing accelerator, 0.2 g) And dissolved by heating. Polymer A (100 g) was added to the solution 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 (hexahydrophthalic anhydride and methylhexahydro A mixture of phthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd. (100 g), tricyclohexylphosphine (curing accelerator, 0.2 g) is added and mixed and degassed for an optical semiconductor device. A sealant was obtained. 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 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 produced in Examples 1-4 and Comparative Examples 1-4, and its hardened | cured material. The results are shown in Table 1.

(1) Measurement of pseudo-absorption coefficient (ε1) of liquid acid anhydride The liquid acid anhydride (1 g) used in Examples and Comparative Examples was dissolved in THF (9 g) and placed in a 1 cm quartz cell, and Hitachi, Ltd. Absorbance (Abs.) At a wavelength of 400 nm was measured using “U-4000” manufactured by Kobayashi. The value was previously placed in a 1 cm quartz cell of THF and the absorbance (Abs.) At a wavelength of 400 nm was subtracted using “U-4000” manufactured by Hitachi, Ltd. as the absorbance (Abs.) Of the liquid acid anhydride. did. Using the absorbance (Abs.) Of the obtained liquid acid anhydride, the pseudo-absorption coefficient (ε1) of the liquid acid anhydride was measured according to the above-described formula (1).

(2) Measurement of Pseudo Absorption Coefficient (ε2) of Curing Accelerator The curing accelerator (1 g) used in Examples and Comparative Examples was dissolved in THF (9 g) and placed in a 1 cm quartz cell, and “U” manufactured by Hitachi, Ltd. -400 "was measured for absorbance (Abs.) At a wavelength of 400 nm. The value obtained by previously adding THF in a 1 cm quartz cell and subtracting the absorbance (Abs.) At a wavelength of 400 nm using “U-4000” manufactured by Hitachi, Ltd. was defined as the absorbance (Abs.) Of the curing accelerator. Using the absorbance (Abs.) Of the obtained curing accelerator, the pseudo-absorption coefficient (ε2) of the curing accelerator was measured according to the above-described formula (2).

(3) Measurement of pseudo-absorption coefficient (ε ′) of mixture of liquid acid anhydride and curing accelerator The curing accelerator (1 g) used in Examples and Comparative Examples was dissolved in liquid acid anhydride (9 g), The absorbance (Abs.) At a wavelength of 400 nm was measured using “U-4000” manufactured by Hitachi, Ltd. in a 1 cm quartz cell. The liquid acid anhydride was preliminarily placed in a 1 cm quartz cell and the absorbance (Abs.) At a wavelength of 400 nm was subtracted using “U-4000” manufactured by Hitachi, Ltd. as the absorbance (Abs.) Of the mixture. . Using the absorbance (Abs.) Of the obtained mixture, the pseudo-absorption coefficient (ε ′) of the mixture was measured according to the above-described formula (3).

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

(5) Light transmittance after heat resistance test A cured product having a thickness of 1 mm was left in an oven at 150 ° C. for 1000 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 .

(6) 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, and irradiated with light of 100 mW / cm ² for 24 hours. The measurement was performed using U-4000 manufactured by the company. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ When less than 10%: ○, When less than 10 to 40%: Δ, When 40 or more: x .

(7) High-temperature energization test, high-temperature and high-humidity energization test (production 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.
To the flaky silver powder-containing polymer (100 g), Rikacid MH-700G (a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)), Shin Nippon Rika Co., Ltd., 3.75 g), Tricyclohexylphosphine (curing accelerator, 0.045 g) was heated and dissolved, 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 are electrically connected with a gold wire, and the sealing agents prepared in Examples and Comparative Examples are injected, and 110 ° C. × 3 hours, 130 ° C. × 3 hours, or 100 ° C. × 3. The optical semiconductor device having the structure shown in FIG. 1 was prepared by curing at 150 ° C. for 3 hours.
The produced optical semiconductor device was put in an oven at 85 ° C., and a high-temperature energization test was conducted at a current value of 10 mA for 1000 hours. Moreover, the produced optical semiconductor device was put into a high-temperature and high-humidity oven at 60 ° C. and 90 RH%, and a high-temperature and high-humidity energization test was conducted at a current value of 10 mA for 1000 hours. The luminance was measured after 1000 hours, and the luminance reduction rate from the initial stage was calculated. When the luminance reduction rate is less than 5%: ◎ When less than 5 to 10%: ○, When less than 10 to 30%: Δ, When 30 or more: × Note that optical semiconductor devices with evaluation results of ◎ and ○ are at a level that does not cause any practical problems.

(8) Adhesion test Sealant for optical semiconductor is applied to aluminum, polyphthalamide resin (PPA), polybutylene terephthalate resin (PBT), and 110 ° C. × 3 hours, 130 ° C. × 3 hours or 100 ° C. × 3 A thin film was prepared by curing at 150 ° C. for 3 hours, and an adhesion test was conducted using a gobang eye adhesion test method. In Table 1, when the number of peels was 0: ◯, when the number of peels 1 to 70: Δ, and when the number of peels 71 to 100: x.

According to the present invention, when used as a sealant for sealing a light emitting element of an optical semiconductor element such as a light emitting diode, the transparency to the housing material or the like enclosing the light emitting element is reduced. A thermosetting composition for optical semiconductors and optical semiconductors, which has excellent light resistance to light of a wavelength and has extremely high heat resistance, and does not cause discoloration due to heat generation of a light emitting element sealed in a cured product. Sealant for device, die bond material for optical semiconductor device, underfill material for optical semiconductor device, thermosetting composition for optical semiconductor, sealant for optical semiconductor device, die bond material for optical semiconductor device and / or optical semiconductor An optical semiconductor element using an element underfill material 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 single pseudo-absorption coefficient when a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (3: 7 (weight ratio)) is used as the liquid acid anhydride, and tricyclohexylphosphine is used as the curing accelerator ( It is a graph which shows the relationship between (epsilon1), ((epsilon) 2), pseudo-absorption coefficient ((epsilon) '), and an irradiation light wavelength. It is the graph which expanded the relationship between pseudo-absorption coefficient ((epsilon) 1) of FIG. 4, ((epsilon) 2), and an irradiation light wavelength.

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 33 for optical semiconductors Bump

Claims (14)

A thermosetting composition for an optical semiconductor containing a silicone resin having at least one cyclic ether-containing group in the molecule, a liquid acid anhydride, and a curing accelerator,
The liquid acid anhydride is represented by the following formula (1), the pseudo-absorption coefficient (ε1) at a wavelength of 400 nm in tetrahydrofuran (THF) at 25 ° C., and the curing accelerator represented by the following formula (2). The pseudo-absorption coefficient (ε2) at a wavelength of 400 nm in tetrahydrofuran (THF) at 25 ° C. is 0.1 or less, and the following formula (3) of the mixture of the liquid acid anhydride and the curing accelerator: And a pseudo-absorption coefficient (ε ′) at 25 ° C. and a wavelength of 400 nm is 0.2 to 10.

2. The optical semiconductor according to claim 1, wherein the liquid acid anhydride is at least one selected from the group consisting of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hydrogenated methylnadic acid anhydride. Thermosetting composition. The thermosetting composition for optical semiconductors according to claim 2, wherein the curing accelerator has a structure represented by the following general formula (1).

In general formula (1), R ′, R ″, and R ′ ″ may be different or the same, and may have a branched or cyclic alkyl group having 1 to 12 carbon atoms. Represents. The silicone resin contains a resin component having an average composition formula represented by the following general formula (2), and the content of the cyclic ether-containing group is 0.1 to 50 mol%. Item 4. The thermosetting composition for optical semiconductors according to item 1, 2 or 3.

In the general formula (2), a, b, c and d are a / (a + b + c + d) = 0 to 0.2, b / (a + b + c + d) = 0.3 to 1.0, c / (a + b + c + d) = 0, respectively. To 0.5, d / (a + b + c + d) = 0 to 0.3, at least one of R ^{1 to} R ⁶ represents a cyclic ether-containing group, and R ^{1 to} R ⁶ other than the cyclic ether-containing group are Represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different from each other. The silicone resin contains a resin component having an average composition formula represented by the following general formula (3), (4), (5), or (6). Stopper thermosetting composition.

In general formula (3), e and f satisfy e / (e + f) = 0.5 to 0.95, f / (e + f) = 0.05 to 0.5, and R ¹² represents a cyclic ether-containing group. R ¹⁰ and R ¹¹ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same or different from each other.

In the general formula (4), g and h satisfy g / (g + h) = 0.5 to 0.95, h / (g + h) = 0.05 to 0.5, and R ¹⁴ and / or R ¹⁵ are , A cyclic ether-containing group, and R ¹³ represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. When only one of R ^{14 and} R ¹⁵ is a cyclic ether, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the general formula (5), i, j and k satisfy (i + j) / (i + j + k) = 0.5 to 0.95, k / (i + j + k) = 0.05 to 0.5, R ¹⁸ and / or Or R ¹⁹ is a cyclic ether-containing group, and R ¹⁶ , R ¹⁷ and R ²⁰ each represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other May be different or different. When only one of R ^{18 and} R ¹⁹ is a cyclic ether, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the general formula (6), l, m and n satisfy 1 / (l + m + n) = 0.5 to 0.95, (m + n) / (l + m + n) = 0.05 to 0.5, and R ²³ is A cyclic ether-containing group, R ²¹ , R ²² , R ²⁴ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as each other; May be different. 6. The thermosetting composition for optical semiconductors according to claim 1, 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 or 6, wherein the cyclic ether-containing group is a glycidyl group and / or an epoxycyclohexyl group. The number average molecular weight of silicone resin is 1000-50,000, The thermosetting composition for optical semiconductors of Claim 1, 2, 3, 4, 5, 6 or 7 characterized by the above-mentioned. Furthermore, the thermosetting composition for optical semiconductors of Claim 1, 2, 3, 4, 5, 6, 7 or 8 characterized by containing the microparticles | fine-particles which have a metal element and / or a metalloid element. 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.

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