JP2008045088A - Thermosetting composition for optical semiconductor, sealant for optical semiconductor element, die bond material for optical semiconductor element, underfill material for optical semiconductor element and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for an optical semiconductor element with high transparency without heat generation of a luminous element or discoloration by emission of light and excellent in heat resistance and light resistance, excellent in adhesion to such as housing materials, and further excellent in heat resistance such as hot and cold cycle and being left unattended under elevated temperatures, a sealant and a die bond material for an optical semiconductor element, and a thermosetting composition and a sealant for the optical semiconductor, an optical semiconductor element using the die bond material for the optical semiconductor element and/or the underfill material for the optical semiconductor element composition. <P>SOLUTION: The thermosetting composition for the optical semiconductor is characterized in that it contains a silicone resin having one or more cyclic ether-containing group in the molecule, the thermosetting agent can react with the cyclic ether-containing group and a layered silicate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention is highly transparent, has no heat generation or discoloration due to light emission, has excellent heat resistance and light resistance, has excellent adhesion to a housing material, etc., and also has heat resistance such as a cold cycle and high temperature storage property. An excellent thermosetting composition for optical semiconductors capable of increasing reliability under high-temperature and high-humidity conditions, an encapsulant for optical semiconductor elements using the same, a die-bonding material for optical semiconductor elements, and the optical semiconductor The present invention relates to an optical semiconductor device using the thermosetting composition for optical semiconductor, the encapsulant for optical semiconductor, the die bond material for optical semiconductor element and / or the underfill material for optical semiconductor element.

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

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

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

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

Silicone resin has a large coefficient of linear expansion, seals the light emitting element, and repeatedly turns on and off, and a thermal cycle is applied, a large internal stress is generated, cracking occurs, and the light emitting element and the lead electrode are bonded. There was a problem that a large stress was applied to the wire to be electrically connected and the wire was cut.
Furthermore, when silicone resin is used as a die bond material or underfill material, the linear expansion coefficient is large, so if the amount of heat generated from a light emitting element such as an LED is large, the light emitting element is distorted and the wire that electrically connects the light emitting element In the case of chipping and flip chip mounting, there have been problems such as bump peeling.
JP 2003-277473 A JP 2002-314142 A

In view of the above situation, the present invention is highly transparent, has no heat generation or discoloration due to light emission, has excellent heat resistance and light resistance, has excellent adhesion to a housing material, etc., and further has a cooling cycle and high temperature storage property. Such a thermosetting composition for optical semiconductors, which has excellent heat resistance and can be highly reliable under high temperature and high humidity conditions, a sealing agent for optical semiconductor elements, a die bond material for optical semiconductor elements, and the like, and An object of the present invention is to provide an optical semiconductor device using the thermosetting composition for optical semiconductors, the encapsulant for optical semiconductors, the die bond material for optical semiconductor elements, and / or the underfill material for optical semiconductor elements. .

The present invention is a thermosetting composition for optical semiconductors, comprising a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a layered silicate. is there.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention have a resin composition containing a silicone resin having a specific structure having one or more cyclic ether-containing groups in the molecule, and a thermosetting agent capable of reacting with the cyclic ether-containing groups. The sealing agent using the product has high transparency to light of a short wavelength in the blue to ultraviolet region, has no heat generation or discoloration due to light emission of the light emitting element to be sealed, and has excellent heat resistance and light resistance, such as a light emitting diode. When used as a sealing agent for sealing a light emitting element of an optical semiconductor element, it has excellent adhesion to a housing material or the like enclosing the light emitting element, and further contains a layered silicate, so that the linear expansion of the sealing agent Even when the rate is reduced and a thermal cycle is applied, it has been found that cracks accompanying an increase in internal stress, cutting of wires connected to optical semiconductor elements, etc. can be prevented, and the present invention has been completed. .

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 preferably contains a resin component whose average composition formula is represented by the following general formula (1).

一般式（１）中、ａ、ｂ、ｃ及びｄは、それぞれａ／（ａ＋ｂ＋ｃ＋ｄ）＝０〜０．２、ｂ／（ａ＋ｂ＋ｃ＋ｄ）＝０．３〜１．０、ｃ／（ａ＋ｂ＋ｃ＋ｄ）＝０〜０．５、ｄ／（ａ＋ｂ＋ｃ＋ｄ）＝０〜０．３を満たし、Ｒ^１〜Ｒ^６は、少なくとも１個が環状エーテル含有基を表し、前記環状エーテル含有基以外のＲ^１〜Ｒ^６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。

In the general formula (1), a, b, c and d are a / (a + b + c + d) = 0 to 0.2, b / (a + b + c + d) = 0.3 to 1.0, c / (a + b + c + d) = 0, 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.

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

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

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

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

In the silicone resin, the preferable lower limit of the content of the cyclic ether-containing group is 0.1 mol%, and the preferable upper limit is 50 mol%. When the content is less than 0.1 mol%, the reactivity between the silicone resin and the thermosetting agent described later is remarkably lowered, and the curability of the thermosetting composition for optical semiconductors of the present invention may be insufficient. . If it exceeds 50 mol%, the cyclic ether-containing group not involved in the reaction between the silicone resin and the thermosetting agent increases, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention may be lowered. A more preferred lower limit is 5 mol%, and a more preferred upper limit is 30 mol%.
In 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 (1), 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 (1), the structural unit represented by (R ⁴ R ⁵ SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following general formula (1-2): That is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxyl group or an alkoxy group.
(R ⁴ R ⁵ SiXO _1/2 ) (1-2)
In the general formula (1-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

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

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

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

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

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

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

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

When the 29Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed on the silicone resin represented by the general formula (1) based on tetramethylsilane (hereinafter referred to as TMS), a slight variation is observed depending on the type of the substituent. However, a peak corresponding to the structural unit represented by (R ¹ R ² R ³ SiO _1/2 ) _a in the general formula (1) appears in the vicinity of +10 to 0 ppm, and (R in the general formula (1) ⁴ R ⁵ SiO _2/2 ) _b and each peak corresponding to the bifunctional structural unit of (1-2) appear in the vicinity of −10 to −30 ppm, and (R ⁶ SiO _3/2 ) of the above general formula (1) _c , peaks corresponding to the trifunctional structural units of (1-3) and (1-4) appear in the vicinity of −50 to −70 ppm, and (SiO _4/2 ) _{d of} the above general formula (1), (1 -5), tetrafunctional structures of (1-6) and (1-7) Each peak corresponding to the position appears in the vicinity of -90~-120ppm.
Therefore, it is possible to measure the ratio of the general formula (1) by measuring 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 (1), 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 Cross-linking 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 (1-2) to (1-7 The same structure as the bifunctional structural unit, trifunctional structural unit and tetrafunctional structural unit represented by

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

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

Specific examples of the resin having a structural unit of R ⁷ R ⁸ SiO _{2/2 and} a structural unit of R ⁹ SiO _3/2 in the skeleton of one molecule of the silicone resin include the following general formulas (2) to ( The resin represented by 5) can be used.

上記一般式（２）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 (2), 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（３）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 (3), 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（４）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 (4), 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（５）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 (5), R ²³ is a cyclic ether-containing group, and R ²¹ , R ²² , and R ^{24 each} 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 (2) or (5). In the general formulas (2) to (5), the cyclic ether-containing group preferably contains either one of a glycidyl group or an epoxycyclohexyl group.

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 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.

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 8 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 (1) described above, preferably What has the structure represented by any of the above general formulas (2) to (5) 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 (6), (7), (8), and (9) or partial hydrolysates thereof.

R ²⁵ R ²⁶ R ²⁷ Si (OR) (6)
R ²⁸ R ²⁹ Si (OR) ₂ (7)
R ³⁰ Si (OR) ₃ (8)
Si (OR) ₄ (9)

In the general formulas (6) to (9), 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 (6) to (9), 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 (6) to (9), 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 (6) to (9) or a partial hydrolyzate thereof is subjected to a condensation reaction with a siloxane compound having a cyclic ether-containing group described later. The silicone resin synthesized in this manner is appropriately adjusted so as to have a structure represented by the above general formula (1), preferably a structure represented by any one of the above general formulas (2) to (5).

Examples of the siloxane compound having a cyclic ether-containing group include an alkoxysilane having a cyclic ether-containing group represented by the following general formula (10) or a partial hydrolyzate thereof.

R ³¹ R ³² _d Si (OR ³³ ) _(3-d) (10)

In the general formula (10), 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 (10), 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 (10), R ³² represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. 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 (1). In the general formula (10), 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 (6).

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

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

The thermosetting composition for optical semiconductors of the present invention contains a layered silicate.
By containing the layered silicate, the linear expansion coefficient of the thermosetting composition for optical semiconductors of the present invention can be reduced.
Here, for example, the linear expansion coefficient of the thermosetting composition for optical semiconductors can also be reduced by containing conventionally known inorganic fillers such as silica, calcium carbonate, and titanium oxide. However, when an inorganic filler in such an amount that the linear expansion coefficient is sufficiently low is contained in the photocurable semiconductor thermosetting composition, when used as a sealant for the optical semiconductor element, the substrate with the optical semiconductor element mounted thereon is used. Problems such as a decrease in adhesive strength and a decrease in handling properties occur. However, the layered silicate can sufficiently reduce the linear expansion coefficient of the thermosetting composition for optical semiconductors in a small amount as compared with the case where the inorganic filler is contained. Therefore, there is no problem in adding the inorganic filler.

The layered silicate means a silicate mineral having an exchangeable cation between layers.
The layered silicate is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite; vermiculite, halloysite, mica, and the like. Among these, at least one selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite is preferably used. The layered silicate may be a natural product or a synthetic product. These layered silicates may be used alone or in combination of two or more.

The shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the preferable upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the preferable upper limit is 1 μm, and the preferable lower limit of the aspect ratio is 20, The preferred upper limit is 500, the more preferred lower limit of the average length is 0.05 μm, the more preferred upper limit is 2 μm, the more preferred lower limit of the thickness is 0.01 μm, the more preferred upper limit is 0.5 μm, the aspect ratio A preferred lower limit is 50, and a more preferred upper limit is 200.

The exchangeable cation existing between the layers of the layered silicate is a metal ion such as sodium or calcium existing in the crystal structure of the layered silicate, and these metal ions are exchanged with a cationic substance. Therefore, various cationic substances can be inserted (intercalated) between the crystal layers of the layered silicate.

The cation exchange capacity of the layered silicate is not particularly limited, but a preferred lower limit is 50 milliequivalent / 100 g, and a preferred upper limit is 200 milliequivalent / 100 g. When the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by cation exchange, so that the crystal layers are not sufficiently depolarized (hydrophobized). In some cases, if it exceeds 200 milliequivalents / 100 g, the bonding strength between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.

In the layered silicate, metal ions contained as exchangeable cations in the crystal structure are preferably exchanged with a cationic surfactant. The layered silicate is hydrophobized, whereby the affinity between the layered silicate and the silicone resin is increased, and the layered silicate can be more uniformly finely dispersed in the silicone resin.

It does not specifically limit as a cationic surfactant inserted between the crystal | crystallization layers of the said layered silicate, For example, a quaternary ammonium salt, a quaternary phosphonium salt, etc. are mentioned. Among them, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms (alkyl ammonium salt having 6 or more carbon atoms) is suitably used because the crystal layer of the layered silicate can be sufficiently nonpolarized (hydrophobized). Used.

The quaternary ammonium salt is not particularly limited, and examples thereof include trimethyl alkyl ammonium salt, triethyl alkyl ammonium salt, tributyl alkyl ammonium salt, dimethyl dialkyl ammonium salt, dibutyl dialkyl ammonium salt, methyl benzyl dialkyl ammonium salt, and dibenzyl dialkyl ammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, quaternary ammonium salt having an aromatic ring, quaternary ammonium salt derived from aromatic amines such as trimethylphenylammonium, and two polyethylene glycol chains Dialkyl quaternary ammonium salt, dialkyl quaternary ammonium salt having two polypropylene glycol chains, polyethylene glycol chain One having trialkyl quaternary ammonium salts, trialkyl quaternary ammonium salt having one polypropylene glycol chain. Of these, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-dimethyl ammonium salt and the like are particularly suitable. is there. These quaternary ammonium salts may be used alone or in combination of two or more.

The quaternary phosphonium salt is not particularly limited. For example, todecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, trioctylmethylphosphonium salt, distearyl Examples thereof include dimethylphosphonium salt and distearyl dibenzylphosphonium salt. These quaternary phosphonium salts may be used alone or in combination of two or more.

The layered silicate can improve dispersibility in the silicone resin by the chemical treatment as described above. The chemical treatment is not limited to a cation exchange method using a cationic surfactant (hereinafter, also referred to as a chemical modification (1) method). For example, chemical modification (2) to chemical modification (6) shown below. It can also be carried out by various chemical treatment methods. These chemical modification methods may be used alone or in combination of two or more. In addition, the layered silicate whose dispersibility in the silicone resin is improved by various chemical treatment methods shown below including the chemical modification (1) method is also referred to as “organized layered silicate”.

In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method can be combined with a functional group or a chemical bond. In this method, chemical treatment is performed with a compound having at least one functional group having high chemical affinity at the molecular end.

In the chemical modification (3) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method can be chemically bonded to a functional group or a chemical bond. In this method, chemical treatment is performed with a compound having one or more functional groups and reactive functional groups having high chemical affinity at the molecular ends.

The chemical modification (4) method is a method in which the crystallized surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.

The chemical modification (5) method is a chemical treatment (4) method in which a chemical treatment is performed with a compound having one or more reactive functional groups in addition to the anion site in the molecular chain of the compound having anionic surface activity.

In the chemical modification (6) method, the organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether type. This is a method using a composition to which a resin having a functional group capable of reacting with a layered silicate such as a resin is added.

In the chemical modification (2) method, the functional group that can be chemically bonded to the hydroxyl group or the functional group having a large chemical affinity without chemical bonding is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, and a carboxyl group. Groups (including dibasic acid anhydrides), hydroxyl groups, isocyanate groups, aldehyde groups and other functional groups, and other functional groups having high chemical affinity with hydroxyl groups. The compound having a functional group that can be chemically bonded to the hydroxyl group or a functional group having a large chemical affinity without chemical bonding is not particularly limited. For example, a silane having the functional group exemplified above. Examples thereof include compounds, titanate compounds, glycidyl compounds, carboxylic acids and alcohols. These compounds may be used alone or in combination of two or more.

The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ- Minopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used alone or in combination of two or more.

In the chemical modification (4) method and the chemical modification (5) method, as a compound having an anionic surface activity, a compound having an anionic surface activity and having one or more reactive functional groups in addition to the anion site in the molecular chain The layer silicate is not particularly limited as long as it can be chemically treated by ionic interaction, for example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate, secondary higher alcohol sulfate, Examples thereof include unsaturated alcohol sulfate salts. These compounds may be used alone or in combination of two or more.

The minimum with the preferable compounding quantity of the said layered silicate is 0.1 weight part with respect to 100 weight part of said silicone resins, and an upper limit is 100 weight part. If the amount is less than 0.1 parts by weight, the linear expansion coefficient of the thermosetting composition for optical semiconductors of the present invention may not be sufficiently reduced, and heat resistance such as cooling cycle and high-temperature storage property is insufficient. May be. When the amount exceeds 100 parts by weight, when used as a sealant for an optical semiconductor element, there may be problems such as a decrease in adhesion to a substrate on which the optical semiconductor element is mounted and a decrease in handling properties. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 50 parts by weight.
The same applies when the layered silicate is the organically modified layered silicate.

In the thermosetting composition for optical semiconductors of the present invention, the layered silicate has an average interlayer distance of (001) plane measured by a wide angle X-ray diffraction measurement method of 3 nm or more, and a part or all of the five layers. It is preferable to be dispersed in the following. More preferably, the average interlayer distance is 3.5 nm or more, and a part or all of the average interlayer distance is dispersed in 5 layers or less.
That the average interlayer distance of the layered silicate is 3 nm or more means that the interlayer of the layered silicate is cleaved by 3 nm or more, and part or all of the layered silicate is 5 layers or less. Dispersing in the layer means that a part or most of the layered silicate laminate is widely dispersed in the thermosetting composition for optical semiconductors of the present invention, both of which are layered silicates. It means that the interaction between salt layers is weakened.

If the average interlaminar distance of the layered silicate is 3 nm or more, preferably 3.5 nm or more, the lamellar silicate crystal flake layers are separated into layers, and the interaction of the layered silicate is so weak that it can be almost ignored. It means that the dispersion state of the crystal flakes constituting the layered silicate in the thermosetting composition for optical semiconductors of the present invention can be sustained stably.
On the other hand, the average interlayer distance of the layered silicate is 3 nm or less, which means that the layered silicate crystal flakes are present in the resin while maintaining interaction with each other, that is, in a state in which dozens of layers are bonded and laminated (aggregated state) This means that a large specific surface area cannot be obtained by laminating into layers. That is, since it is difficult to obtain the effect of being a lamellar flake, the effect of high peeling and high dispersion may not be obtained.

Further, that part or all of the layered silicate is dispersed in 5 layers or less specifically means that 10% or more of the layered silicate is dispersed in 5 layers or less. Preferably, 20% or more of the layered silicate is dispersed in 5 layers or less. The number of layered silicate layers is preferably 5 layers or less, more preferably 3 layers or less.

In the thermosetting composition for optical semiconductors of the present invention, the average interlayer distance of the layered silicate is 3 nm or more, and a part or all of the layered silicate is dispersed in 5 layers or less, that is, a resin If the layered silicate is highly dispersed therein, the interface area between the resin and the layered silicate increases, and the average distance between crystal flakes of the layered silicate decreases. When the interface area between the resin and the layered silicate increases, the degree of resin restraint on the surface of the layered silicate increases, and the linear expansion coefficient decreases.

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

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

The thermosetting composition for optical semiconductors of the present invention 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.

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 50000 mPa * s. When 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. When the optical semiconductor element exceeds 50000 mPa · s, the optical semiconductor element is uniform and accurate. 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 comprises a silicone resin having one or more cyclic ether-containing groups in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing groups, and a layered silicate. High transparency, no discoloration due to heat generation or emission of light emitting elements, excellent heat resistance and light resistance, excellent adhesion to housing materials, etc., excellent heat resistance such as cold cycle and high temperature storage, high temperature and high temperature Reliability under wet conditions can be increased.

The method for producing the thermosetting composition for optical semiconductors of the present invention is not particularly limited, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three-roll, a bead mill, Examples include a method of mixing predetermined amounts of the above-described silicone resin, thermosetting agent, 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.
An encapsulant for optical semiconductor elements using the thermosetting composition for optical semiconductors of the present invention is also one aspect of the present 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)
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, so that it has excellent heat resistance, light resistance and adhesiveness, and even when subjected to a thermal cycle, it is cracked. Will not occur. 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.
As the metal-coated particles, for example, particles obtained by applying gold or silver plating to resin particles are preferable. Specific examples include Micropearl AU (manufactured by Sekisui Chemical Co., Ltd.) in which a gold layer is formed on the surface of organic fine particles.

Moreover, when the microparticles | fine-particles 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. In addition, you may use the metal coating particle which formed the gold layer, the silver layer, the copper layer, etc. on the surface of the resin particle mentioned above, for example, micropearl AU (Sekisui Chemical Co., Ltd.) which formed the gold layer on the surface of the organic fine particle. Can be used.

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 device 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 using 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 contains a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a layered silicate. Therefore, it is highly permeable to light with a short wavelength in the blue to ultraviolet region, and when used as an encapsulant for an optical semiconductor element, the light emitting element to be sealed has no heat generation or discoloration due to light emission, and has excellent light resistance, and a light emitting diode When the light emitting element of the optical semiconductor device is sealed, the optical semiconductor device has excellent adhesion to the housing material, etc., and also has excellent heat resistance such as a cold cycle and high temperature leaving property, under high temperature and high humidity conditions. The reliability of can be increased.
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 device is also one aspect of the present invention.

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

In the optical semiconductor device shown in FIG. 1, the light emitting element 11 is installed on the heat sink 16 via the die bonding material 10 for an optical semiconductor element 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 device 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 gold, silver, and copper described above. Indicates.
In the optical semiconductor device 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 device of the present invention shown in FIG. 3, the light emitting element 31 is installed via the bump 33, and the underfill material 30 for the optical semiconductor element 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 device of the present invention shown in FIG. 3, the underfill material 30 for an 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 device of the present invention include a light emitting diode, a semiconductor laser, and a photocoupler. Such an optical semiconductor device 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 copying machine, a measurement light source for a vehicle, a signal light, a display light, a display device, and a planar light emission It can be suitably used for body light sources, displays, decorations, various lights, switching elements and the like.

According to the present invention, the transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, the heat resistance and the light resistance are excellent, the adhesiveness to the housing material etc. is excellent, and further the heat resistance such as the cooling cycle and the high temperature leaving property. A thermosetting composition for optical semiconductors, a sealing compound for optical semiconductor elements, a die-bonding material for optical semiconductor elements, an underfill material for optical semiconductor elements, In addition, an optical semiconductor device comprising the optical semiconductor thermosetting composition, an optical semiconductor element sealant, an optical semiconductor element die-bonding material, and / or an optical semiconductor element 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 (400 g), methoxytrimethylsilane (100 g), and 3-glycidoxypropyltrimethoxysilane (100 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer B. The molecular weight of the polymer B is Mn = 3200, Mw = 5400, and (Me ₂ SiO _2/2 ) _0.71 (MeSiO _3/2 ) _0.18 (EpSiO _3/2 ) _0.11 from 29Si-NMR.
3-glycidoxypropyl group content is 15 mol%, epoxy equivalent is 780 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.

(Synthesis Example 4)
In a separable flask with a 2000 mL thermometer and a dropping device, dimethyldimethoxysilane (400 g), methoxytrimethylsilane (50 g), tetramethoxysilane (50 g), and 3-glycidoxypropyltrimethoxysilane (100 g) are placed at 50 ° C. And stirred. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer D. The molecular weight of the polymer D is Mn = 2600, Mw = 3600, and (Me ₂ SiO _2/2 ) _0.73 (MeSiO _3/2 ) _0.09 (EpSiO _3/2 ) _0.10 (SiO ₂ ) from 29Si-NMR. _4/2 ) _0.08
The 3-glycidoxypropyl group content was 14 mol% and the epoxy equivalent was 760 g / eq. Met. The molecular weight and epoxy equivalent of polymer D were determined in the same manner as in Synthesis Example 1.

(Example 1)
Synthetic hectorite (manufactured by Co-op Chemical Co., Lucentite SPN, 30 g) and isopropyl alcohol (100 g) treated with methyl diethylammonium salt were added to polymer A (300 g), and the mixture was stirred with a bead mill until clear. Volatile components were removed from the solution under reduced pressure to prepare dispersion solution A. Dispersed solution A (100 g) was mixed with Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g) and U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g). It performed and obtained the sealing agent for optical semiconductor elements. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

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

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

Example 4
Except having used polymer D instead of polymer A, it carried out similarly to Example 1, and obtained the sealing agent for optical semiconductor elements, and its hardened | cured material.

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

(Comparative Example 2)
Celoxide 2021 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, 50 g), YX-8000 (hydrogenated bisphenol A epoxy resin, manufactured by Japan Epoxy Resin, 50 g), Ricacid MH-700G (manufactured by Nippon Nippon Chemical Co., Ltd., 100 g) U-CAT SA 102 (manufactured by Sun Apro, 0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled 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.

(Comparative Example 3)
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 1-3, and its hardened | cured material. The results are shown in Table 1.

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

(2) Light transmittance after light resistance test A cured product with a thickness of 1 mm is attached to a high-pressure mercury lamp with a filter that cuts 340 nm or less, irradiated at 100 mW / cm ² for 24 hours, and has a light transmittance of 400 nm. The measurement was performed using U-4000 manufactured by the company. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 10%: ○, when less than 10-40%: Δ, when 40 or more: x.

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

(4) Adhesion test Sealants for optical semiconductor elements prepared in Examples and Comparative Examples were applied to aluminum, polyphthalamide resin (PPA), and polybutylene terephthalate resin (PBT), and 100 ° C. × 3 hours, 130 A thin film was prepared by curing at 3 ° C. for 3 hours, and an adhesion test was performed using a cross-cut tape method with a clearance of 1 mm and 100 squares in accordance with JIS K-5400.
In Table 1, when the number of peels was 0: ◯, when the number of peels 1 to 70: Δ, and when the number of peels 71 to 100: x.

(5) Thermal cycle test (production of die bond material for optical semiconductor elements)
Synthetic hectorite (manufactured by Co-op Chemical Co., Lucentite SPN, 30 g) and isopropyl alcohol (100 g), which were organically treated with methyl diethylammonium salt, were added to polymer B (300 g) and stirred with a bead mill until clear. Volatile components were removed from the solution under reduced pressure to prepare a dispersion solution. Flaky silver powder (170 g) having an average particle size of 3 μm and a maximum particle size of 20 μm was added to the dispersion solution (30 g), and the mixture was stirred and kneaded using a three roll.
The flaky silver powder-containing polymer (100 g) was added with Ricacid MH-700G (anhydride, Shin Nippon Chemical Co., Ltd., 3.75 g), U-CAT SA 102 (curing accelerator, San Apro Co., Ltd., 0.075 g). The mixture was 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 100 ° C. × 3 hours, 130 ° C. × 3 hours, or 150 ° C. × 3. The optical semiconductor device having the structure shown in FIG. The optical semiconductor device was subjected to 500 cycles of cooling and heating at −40 ° C. for 30 minutes and 120 ° C. for 30 minutes to confirm the number of wire breaks (cooling cycle test).

(6) High temperature and high humidity test (decrease in brightness)
The produced optical semiconductor device was placed in a high-temperature and high-humidity oven at 60 ° C. and 90 RH% and left 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 10%: ◯, when less than 10-30%: Δ, when 30 or more: x.

(7) Diffraction peak obtained from diffraction of layered surface of layered silicate (synthetic hectorite) in the cured product using an average interlayer distance X-ray diffraction measurement apparatus (Rigaku Corporation, RINT1100) of layered silicate 2θ was measured, the (001) plane distance d of the layered silicate was calculated by the following black diffraction formula, and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ
In the formula, λ is 0.154 nm, and θ represents a diffraction angle.

(8) Ratio of layered silicate dispersed as a laminate of 5 layers or less Cut out the produced cured product with a diamond cutter and photograph using a transmission electron microscope (JEM-1200EXII, manufactured by JEOL Ltd.) The number of dispersed layers of the layered silicate aggregate per unit area was measured, and the ratio (%) of the layered silicate dispersed in 5 layers or less was calculated.

According to the present invention, the transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, the heat resistance and the light resistance are excellent, the adhesiveness to the housing material etc. is excellent, and further the heat resistance such as the cooling cycle and the high temperature leaving property. , A thermosetting composition for optical semiconductors that can be highly reliable under high temperature and high humidity conditions, an encapsulant for optical semiconductor elements, a die bond material for optical semiconductor elements, and an optical semiconductor element Provided are an underfill material, and an optical semiconductor element using the thermosetting composition for optical semiconductor, the encapsulant for optical semiconductor, a die bond material for optical semiconductor element, and / or an underfill material for optical semiconductor element. be able to.

It is sectional drawing which shows typically an example of the optical semiconductor device which uses 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 device which uses 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 device formed using the sealing agent for optical semiconductors of this invention, and the underfill material for optical semiconductor elements.

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 (15)

A thermosetting composition for an optical semiconductor, comprising: a silicone resin having at least one cyclic ether-containing group in a molecule; a thermosetting agent capable of reacting with the cyclic ether-containing group; and a layered silicate. . The silicone resin contains a resin component having an average composition formula represented by the following general formula (1), and the cyclic ether-containing group content is 0.1 to 50 mol%. The thermosetting composition for optical semiconductors according to 1.

In the general formula (1), a, b, c and d are a / (a + b + c + d) = 0 to 0.2, b / (a + b + c + d) = 0.3 to 1.0, c / (a + b + c + d) = 0, 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. 3. The optical resin according to claim 1, wherein the silicone resin contains a resin component having an average composition formula represented by the following general formula (2), (3), (4) or (5). Thermosetting composition.

In general formula (2), e and f satisfy e / (e + f) = 0.5 to 0.95 and 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 (3), 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 (4), 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 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 (5), 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. 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, or 4, wherein the cyclic ether-containing group is a glycidyl group and / or an epoxycyclohexyl group. 6. The thermosetting composition for optical semiconductors according to claim 1, wherein the number average molecular weight of the silicone resin is 1000 to 50,000. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, or 6, wherein the thermosetting agent is an acid anhydride. The light according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite. Thermosetting composition for semiconductor. 9. The metal ion contained as an exchangeable cation in the crystal structure of the layered silicate is exchanged with a cationic surfactant. The thermosetting composition for optical semiconductors as described. The thermosetting composition for optical semiconductors according to claim 1, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms. . An encapsulant for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. 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, 9 or 10. Furthermore, the die-bonding material for optical semiconductors of Claim 12 containing high heat conductive microparticles | 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, 9 or 10. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, the encapsulant for optical semiconductor elements according to claim 11, or claim 12 or 13. 15. An optical semiconductor device comprising the die bonding material for an optical semiconductor element according to claim 14 and / or the underfill material for an optical semiconductor element according to claim 14.

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