JP2009185131A - Thermosetting composition for optical semiconductor, sealing agent for optical semiconductor element, and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for optical semiconductors that is highly transparent, suffers from no discoloration caused by heat evolution or light emission by a light-emitting element to assure excellent heat resistance and light resistance, exhibits excellent adhesion to a housing material or a metal electrode material, and prevents occurrence of cracks under a reflow condition or a heat cycle, and the like. <P>SOLUTION: The thermosetting composition for optical semiconductors comprises a silicone resin bearing a cyclic ether-containing group, a thermosetting agent reactive with the cyclic ether-containing group, and a specific organosilicon compound bearing an SH group and/or a specific organosilicon compound bearing an oxygen-containing heterocycle, where the silicone resin is mainly composed of structural units represented by general formulae (3) and (4) and has a content of the cyclic ether-containing group of 5-40 mol%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention is highly transparent, has no heat generation or discoloration due to light emission, and has excellent heat resistance and light resistance, as well as excellent adhesion to housing materials and metal electrode materials, and cracks under reflow conditions and temperature cycles. The present invention relates to a thermosetting composition for optical semiconductors, an encapsulant for optical semiconductor elements, and an optical semiconductor device.

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. Resins constituting a sealant that seals such a light emitting element are required to have high adhesive strength and excellent mechanical durability, high heat resistance, and high light resistance. And as heat resistance, both heat resistance in the mechanical aspect such as crack prevention in the thermal environment and heat resistance in the coloring aspect that does not discolor or yellow even in the thermal environment are required. .

In recent years, LEDs have come to be used in applications that require high brightness such as automotive headlights and lighting. Therefore, the encapsulant that seals the light emitting element has a large amount of heat generated during lighting. A higher level of heat resistance that can withstand the increase and a higher level of light resistance that prevents light deterioration associated with higher brightness have been demanded.
As such a sealing agent, for example, Patent Document 1 discloses a resin composition containing an epoxy resin such as a bisphenol type epoxy resin or an alicyclic epoxy resin, and an acid anhydride curing agent. Sealants using such a resin composition have high adhesive strength and excellent mechanical durability.
However, it has been difficult to say that a conventional sealant made of an epoxy resin has sufficient heat resistance and light resistance in terms of coloring. Further, it cannot be said that cracks during reflow can be sufficiently prevented, and the heat resistance is not sufficient.

On the other hand, Patent Document 2 discloses a sealant using a silicone resin having a specific epoxy equivalent for the purpose of preventing cracks during reflow. And according to the Example disclosed by patent document 2, after leaving 10 evaluation samples in a 30 degreeC and 70 RH% environment for one week, "preheating 180-200 degreeC, within 120 second, solder temperature When the reflow condition of “260 ° C. within 10 seconds” is passed three times, it is described that the occurrence of cracks was zero.
However, such a silicone resin has a problem in that the adhesion to the metal electrode portion is insufficient or the heat resistance is deteriorated.

In recent years, an optical semiconductor device having a large package area, such as a top view type, is becoming mainstream. In such an optical semiconductor device, when the metal electrode portion is provided largely in order to ensure reflectance, peeling tends to occur near the boundary between the metal electrode portion and the housing material.
In order to solve such a peeling problem, it is necessary to ensure good adhesion between the metal electrode portion and the housing material, but a sealant that satisfies this property has not yet been obtained.
JP 2003-277473 A JP 2006-225515 A

In view of the above situation, the present invention has high transparency, no heat generation of the light emitting element and no discoloration due to light emission, excellent heat resistance and light resistance, excellent adhesion to a housing material or a metal electrode material, It aims at providing the thermosetting composition for optical semiconductors which can prevent generation | occurrence | production of the crack in a temperature cycle, the sealing agent for optical semiconductor elements, and an optical semiconductor device.

As a result of intensive studies, the present inventors have obtained thermosetting for optical semiconductors obtained by using a compound having a predetermined structure as a coupling agent in addition to a silicone resin having a cyclic ether-containing group and a thermosetting agent. When the composition is used as a thermosetting sealant for optical semiconductors, the adhesive force can be dramatically improved. Even if the package material for optical semiconductor elements is enlarged, the metal electrode portion and the housing material It has been found that it is possible to effectively prevent peeling between the two, and the present invention has been completed.

The present invention includes a silicone resin having a cyclic ether-containing group, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a compound represented by the following general formula (1) or (2): It is a thermosetting composition for optical semiconductors, wherein the silicone resin is composed mainly of a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4): When the total number of structural units included is 1, the content of the structural unit represented by the general formula (3) is 0.6 to 0.95 (molar conversion), and is represented by the general formula (4). The content of the structural unit is 0.05 to 0.4 (mol conversion), and the content of the cyclic ether-containing group is 5 to 40 mol%.

In General Formula (1), R ^a represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ^b represents a hydrocarbon group having 1 to 8 carbon atoms, and R ^c represents 1 to 1 carbon atoms. 5 represents an alkyl group, and n represents 1 to 3.

In the general formula (3) and ^(4), R 1, ^{R 2} and ^{R 3} is at least one represents a cyclic ether-containing group, ^R 1, ^{R 2} and ^{R 3} other than the cyclic ether-containing group, the carbon Represents a hydrocarbon of formula 1 to 8 or a fluorinated product thereof, which may be the same or different from each other, and furthermore, in the repeating structure in the silicone resin skeleton, a plurality of different types of R ¹ , R ² and R ³ may be contained.
Hereinafter, the present invention will be described in detail.

The thermosetting composition for optical semiconductors of the present invention contains a compound represented by the above general formula (1) and / or a compound represented by the above general formula (2).
By using the compound represented by the general formula (1) and / or the compound represented by the general formula (2) as a coupling agent, for example, a top view type optical semiconductor element or the like has a large package area, In addition, even when the metal exposed portion such as the metal electrode portion is used in a package having a large size, it is possible to prevent peeling between the metal electrode portion and the package material. In general, as a coupling agent for improving the adhesive force, various compounds other than the compound represented by the general formula (1) and the compound represented by the general formula (2) can be considered. Only when the compound represented by 1) and / or the compound represented by the above general formula (2) is used, the resulting thermosetting composition for an optical semiconductor is used as an encapsulant for an optical semiconductor. , The adhesive strength can be dramatically improved.
Especially, it is preferable to use the compound represented by the said General formula (1). By using the compound represented by the general formula (1), in addition to improving the adhesive force, the wire reliability is extremely excellent.
In addition, in this specification, wire reliability means that wire breakage does not occur.

Although it does not specifically limit as a compound represented by the said General formula (1), For example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxymethoxysilane, 3-mercaptopropyl Examples include methyldiethoxysilane.

Although it does not specifically limit as a compounding quantity of the compound represented by the said General formula (1), A preferable minimum is 0.01 weight part and a preferable upper limit is 3 weight part with respect to a total of 100 weight part of a silicone resin. If it is less than 0.01 part by weight, peeling may not be suppressed, and if it exceeds 3 parts by weight, it may cause a void. A more preferred lower limit is 0.05 parts by weight, and a more preferred upper limit is 2 parts by weight.

The compound represented by the general formula (2) is not particularly limited, and examples thereof include 3-trimethoxysilylpropyl succinic acid and 3-triethoxysilylpropyl succinic acid.

Although it does not specifically limit as a compounding quantity of the compound represented by the said General formula (2), A preferable minimum is 0.01 weight part and a preferable upper limit is 3 weight part with respect to a total of 100 weight part of a silicone resin. If it is less than 0.01 part by weight, peeling may not be suppressed, and if it exceeds 3 parts by weight, it may cause a void. A more preferred lower limit is 0.05 parts by weight, and a more preferred upper limit is 2 parts by weight.

The compound represented by the general formula (1) and the compound represented by the general formula (2) may be reacted in advance to have a high molecular weight.

The thermosetting composition for optical semiconductors of the present invention contains a silicone resin having a cyclic ether-containing group.
In the thermosetting composition for optical semiconductors of the present invention, the silicone resin contains a structural unit represented by the general formula (3) and a structural unit represented by the general formula (4) as main components. In this specification, “having as a main component” means that the silicone resin is composed of only the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4). However, as long as the effects of the present invention are not impaired, the structural unit represented by the general formula (3) and other structural units other than the structural unit represented by the general formula (4) It may mean that it may have.

Further, when the total number of structural units contained in the silicone resin is 1, the lower limit of the content of the structural unit represented by the general formula (3) is 0.6, and the upper limit is 0.95 (molar conversion). The lower limit of the content of the structural unit represented by the general formula (4) is 0.05, and the upper limit is 0.4 (molar conversion). By containing a silicone resin having a cyclic ether-containing group and containing the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) in the above range, the light of the present invention The thermosetting composition for semiconductors has a high transmittance with respect to light having a short wavelength in the blue to ultraviolet region, and when used as a sealing agent for an optical semiconductor element, heat generation of the light-emitting element to be sealed and film reduction due to light emission or There is no discoloration and excellent heat resistance and light resistance, and when the light emitting element of an optical semiconductor element such as a light emitting diode is sealed, the optical semiconductor element has excellent adhesion to a housing material or the like.

In the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4), at least one of R ^{1 to} R ³ 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 lower limit of the content of the cyclic ether-containing group is 5 mol%, and the upper limit is 40 mol%. If it is less than 5 mol%, the reactivity between the silicone resin and the thermosetting agent described later is remarkably lowered, and the curability of the photocurable semiconductor thermosetting composition of the present invention becomes insufficient. If it exceeds 40 mol%, the number of cyclic ether-containing groups not involved in the reaction between the silicone resin and the thermosetting agent will increase, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention will decrease. A preferable lower limit is 7 mol%, and a preferable upper limit is 30 mol%.
In addition, in this specification, content of the said cyclic ether containing group means the quantity of the said cyclic ether containing group contained in the average composition of the said silicone resin component.

In the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4), R ^{1 to} R ³ other than the cyclic ether-containing group are carbon atoms having 1 to 8 carbon atoms. Represents hydrogen or a fluoride thereof.

It does not specifically limit as said C1-C8 hydrocarbon, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group and the like can be mentioned.

In the silicone resin, the structural unit represented by the general formula (3) (hereinafter also referred to as a bifunctional structural unit) is a structure represented by the following general formula (3-2), that is, in the bifunctional structural unit. One of the oxygen atoms bonded to the silicon atom is a structure in which a hydroxyl group or an alkoxy group is formed.
(R ¹ R ² SiXO _1/2 ) (3-2)
In the general formula (3-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

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

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

When the above-mentioned silicone resin is subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation is observed depending on the type of substituent, the above general formula (3 ) And (3-2) corresponding to the bifunctional structural unit appear in the vicinity of −10 to −30 ppm, and the trifunctional structural unit of the above general formulas (4), (4-2) and (4-3) Each peak corresponding to appears in the vicinity of −50 to −70 ppm.
Therefore, it is possible to measure the ratio of the silicone resin by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.
However, when the ²⁹ Si-NMR measurement based on the TMS cannot be distinguished from the bifunctional structural unit of the general formula (3), not only the ²⁹ Si-NMR measurement result but also ¹ H-NMR The ratio of structural units can be discriminated by using the results measured by ¹⁹ F-NMR or the like as necessary.

It is preferable that the average composition formula of such a silicone resin mainly composed of a bifunctional structural unit and a trifunctional structural unit is represented by the following general formula (5), (6) or (7). In addition, the said silicone resin has an average composition formula represented by the following general formula (5), (6) or (7) that the thermosetting composition for optical semiconductors of the present invention is represented by the following general formula. (5) When it is a mixture containing not only the resin component represented by (6) or (7) but also a resin component having various structures, the average composition of the resin components contained This also means the case represented by the following general formula (5), (6) or (7).

In general formula (5), a and b satisfy a / (a + b) = 0.6 to 0.95, b / (a + b) = 0.05 to 0.4, and any one of R ^{4 to} R ⁶ Is a cyclic ether-containing group, and R ^{4 to} R ⁶ other than the cyclic ether-containing group are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, which may be the same or different from each other. .

In the general formula (6), c, d and e satisfy (c + d) / (c + d + e) = 0.6 to 0.95, e / (c + d + e) = 0.05 to 0.4, and R ^{7 to} R ¹¹ is a cyclic ether-containing group, and R ^{7 to} R ¹¹ other than the cyclic ether-containing group are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, which may be the same as or different from each other. It may be. However, (R ⁷ R ⁸ SiO _2/2 ) and (R ⁹ R ¹⁰ SiO _2/2 ) have different structures.

In general formula (7), f, g, and h satisfy f / (f + g + h) = 0.6 to 0.95, (g + h) / (f + g + h) = 0.05 to 0.4, and R ^{12 to} R ¹⁵ is a cyclic ether-containing group, and R ^{12 to} R ¹⁵ other than the cyclic ether-containing group are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, which may be the same as or different from each other. It may be. However, (R ¹⁴ SiO _3/2 ) and (R ¹⁵ SiO _3/2 ) have different structures.

In the thermosetting composition for optical semiconductors of the present invention, the silicone resin preferably has a cyclic ether-containing group and a polysiloxane skeleton bonded via a silicon-carbon bond. Since the cyclic ether-containing group and the polysiloxane skeleton are bonded via a silicon-carbon bond, the thermosetting composition for optical semiconductors of the present invention is excellent in light resistance and is preferable. For example, when a resin obtained by an addition reaction in which an OH group is reacted is used, a cyclic ether-containing group and a polysiloxane skeleton are bonded via a silicon-oxygen bond. In some cases, sufficient light resistance cannot be obtained.

Moreover, it is preferable that the said silicone resin has a cyclic ether containing group in the structural unit represented by the said General formula (4), ie, a trifunctional structural unit. When the cyclic ether-containing group is contained in the trifunctional structure, the cyclic ether-containing group is likely to be exposed outside the polysiloxane skeleton of the silicone resin, and the cured product of the thermosetting composition for optical semiconductors of the present invention is sufficient. Taking a three-dimensional cross-linking structure makes the heat resistance sufficient, and it is possible to suitably prevent film loss in the cured product.

Specifically, the silicone resin in which the cyclic ether-containing group is bonded to a trifunctional structural unit is preferably represented by, for example, the following average formula (8), (9), or (10). .

In general formula (8), i and j satisfy i / (i + j) = 0.6 to 0.95, j / (i + j) = 0.05 to 0.4, and R ¹⁸ is a cyclic ether-containing group. R ¹⁶ and R ¹⁷ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different from each other.

In general formula (9), k, l and m satisfy (k + l) / (k + l + m) = 0.6 to 0.95, m / (k + l + m) = 0.05 to 0.4, and R ²³ is cyclic. It is an ether-containing group, and R ^{19 to} R ²² are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different. However, (R ¹⁹ R ²⁰ SiO _2/2 ) and (R ²¹ R ²² SiO _2/2 ) have different structures.

In general formula (10), n, o, and p satisfy n / (n + o + p) = 0.6 to 0.95, satisfy (o + p) / (n + o + p) = 0.05 to 0.4, and R ²⁶ Is a cyclic ether-containing group, and R ²⁴ , R ²⁵ and R ²⁷ are hydrocarbons or fluorinated compounds having 1 to 8 carbon atoms, and these may be the same or different.

If the silicone resin is composed mainly of the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4), structural units other than these structural units may be used. You may have. In this case, when the total number of structural units contained in the silicone resin is 1, the total content of the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) A preferred lower limit is 0.9 (molar conversion). When it is less than 0.9 (molar conversion), the effects such as excellent heat resistance, light resistance, and adhesion of the thermosetting composition for optical semiconductors of the present invention may be significantly impaired. A more preferred lower limit is 0.95 (molar conversion).

The structural unit other than the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) which may be contained in the silicone resin is not particularly limited. The structural unit represented by (11) or Chemical formula (12) is mentioned.

In the general formula (11), R ²⁸ , R ²⁹ and R ³⁰ represent a cyclic ether-containing group, a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as each other, May be different.

When the silicone resin contains the structural unit represented by the general formula (11) or the chemical formula (12), the content thereof may be the structural unit represented by the general formula (3) and the general formula. There is no particular limitation as long as the total content of the structural units represented by (4) falls within the above-described range. For example, when the total number of structural units contained in the silicone resin is 1, The upper limit with preferable content of the structural unit represented by General formula (11) is 0.1 (mol conversion). The upper limit with preferable content of the structural unit represented by the said Chemical formula (12) is 0.1 (mol conversion). When content of the structural unit represented by the said General formula (11) exceeds 0.1 (mol conversion), the heat resistance of the thermosetting composition for optical semiconductors of this invention may deteriorate. Moreover, when the content of the structural unit represented by the chemical formula (12) exceeds 0.1, it becomes difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention, It may be difficult to maintain the adhesion.

The structural unit represented by the general formula (12) (hereinafter also referred to as a tetrafunctional structural unit) is represented by the following general formula (12-2), (12-3) or (12-4). A structure, that is, a structure in which three or two oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit constitute a hydroxyl group or an alkoxy group, or one of oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit One of which constitutes a hydroxyl group or an alkoxy group.
(SiX ₃ O _1/2 ) (12-2)
(SiX ₂ O _2/2 ) (12-3)
(SiXO _3/2 ) (12-4)

In the general formulas (12-2), (12-3), and (12-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. To express.

In the general formulas (12-2) to (12-4), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and an n-propoxy group. N-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

In the thermosetting composition for optical semiconductors of the present invention, the silicone resin preferably contains an alkoxy group in a range where the lower limit is 0.5 mol% and the upper limit is 10 mol%. By containing such an alkoxy group, the heat resistance and light resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention are dramatically improved. This is presumably because the curing rate can be drastically improved by containing an alkoxy group in the silicone resin, thereby preventing thermal deterioration during curing.
In addition, since the curing speed is dramatically improved as described above, sufficient curability can be obtained even with a relatively small addition amount when a curing accelerator is added.

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

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

In the thermosetting composition for optical semiconductors of the present invention, the preferable lower limit of the number average molecular weight (Mn) of the silicone resin is 1000, and the preferable upper limit is 50,000. If it is less than 1000, volatile components increase at the time of thermosetting, and film loss increases when used as a sealant, which is not preferable. If it exceeds 50,000, viscosity adjustment becomes difficult, which is not preferable. A more preferred lower limit is 1500, and a more preferred upper limit is 15000.
In the present specification, the number average molecular weight (Mn) is a value obtained using polystyrene as a standard using gel permeation chromatography (GPC), and is a measuring device manufactured by Waters (column: manufactured by Showa Denko KK). It means a value measured using Shodex GPC LF-804 (length: 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene.

The method for synthesizing the silicone resin is not particularly limited. For example, (1) a substituent is introduced by a hydrosilylation reaction between a silicone resin (a) having a SiH group and a vinyl compound having a cyclic ether-containing group. Examples thereof include (2) a method in which 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.

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

In the method (2), examples of the siloxane compound include alkoxysilanes having a siloxane unit represented by the following general formulas (13) and (14) or partial hydrolysates thereof.

In the general formulas (13) and (14), R ^{31 to} R ³³ represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched carbon having 1 to 4 carbon atoms. Represents an alkoxy group.

In the general formulas (13) and (14), when R ^{31 to} R ³³ are hydrocarbons having 1 to 8 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, n- Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, An isohexyl group etc. are mentioned.

Further, in the general formulas (13) and (14), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, an ethoxy group, n -Propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

In the above siloxane compound, the compounding ratio of the alkoxysilane having a siloxane unit represented by the general formulas (13) and (14) 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 above has a structure having the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4), preferably the general formulas (8) to (10). It adjusts suitably so that it may become the structure represented by either.

Examples of the siloxane compound having a cyclic ether-containing group include alkoxysilanes having a cyclic ether-containing group represented by the following general formulas (15-1) and (15-2) or partial hydrolysates thereof.

In the general formulas (15-1) and (15-2), R ³⁴ and / or R ³⁵ and R ³⁶ are cyclic ether groups, and only one of R ^{34 and} R ³⁵ is a cyclic ether group. The other represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In general formulas (15-1) and (15-2), the cyclic ether-containing group represented by R ³⁴ and / or R ³⁵ , R ³⁶ is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane. Groups and the like. 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 (15-1), when only one of R ^{34 and} R ³⁵ is a cyclic ether group and the other is a hydrocarbon having 1 to 8 carbon atoms, specifically, for example, a methyl group, Ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group Group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, phenyl group and the like.

In the general formulas (15-1) and (15-2), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, Examples include ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

Specific examples of the compound represented by the general formula (15-1) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3- Glycidoxypropyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyl (methyl) diethoxysilane.

Specific examples of the compound represented by the general formula (15-2) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

In the method (2), as a specific method for the condensation reaction of the siloxane compound and the siloxane compound having a cyclic ether-containing group, for example, the siloxane compound and the siloxane compound having a cyclic ether-containing group are mixed with water, and And a method of synthesizing a silicone resin by reacting in the presence of an acid or basic catalyst.

The compound having the cyclic ether-containing group has a lower limit of 5 mol% and an upper limit of the cyclic ether-containing group based on all organic groups bonded to the silicon atom of the siloxane compound and the siloxane compound having the cyclic ether-containing group. It mix | blends so that it may become 40 mol%.

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, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, cesium hydroxide; Examples include alkali metal alkoxides such as sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide; and alkali metal silanol compounds such as sodium silanolate compounds, potassium silanolate compounds, and cesium silanolate compounds. Of these, potassium-based catalysts and cesium-based catalysts are preferred.

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

In the condensation reaction, an organic solvent may be used because it can prevent the silicone resin to be synthesized from precipitating from the reaction system and can remove the water and free water by the condensation reaction by azeotropic distillation.
The organic solvent is not particularly limited and conventionally known ones can be used alone or in combination. Among them, aromatic organic solvents such as toluene and xylene are preferable.

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

As a method for synthesizing the silicone resin, the method (2) is preferable.
In the method (2), the alkoxy group can be brought into an appropriate range by adjusting the reaction temperature, reaction time, catalyst amount and water amount.

The thermal constituent composition for optical semiconductors of the present invention preferably further contains a bifunctional silicone resin (hereinafter also simply referred to as a bifunctional silicone resin) having one or more glycidyl-containing groups in the molecule.
By blending such a bifunctional silicone resin, the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention is significantly improved. This is because, in the cured product, the bifunctional silicone resin having a flexible skeleton compared to the silicone resin in the gap between the crosslinking points generated by the reaction of the cyclic ether-containing group of the silicone resin having a cyclic ether-containing group in the molecule. It is guessed that this is because it enters.

In the present specification, the glycidyl-containing group only needs to contain a glycidyl group as at least a part of the group. For example, the glycidyl group may contain another skeleton such as an alkyl group or an alkyl ether group and a glycidyl group. Means.

The bifunctional silicone resin having one or more such glycidyl-containing groups in the molecule is not particularly limited, but may contain a resin component whose average composition formula is represented by the following general formulas (16) to (19). preferable. When the bifunctional silicone resin contains a resin component represented by the following general formulas (16) to (19), the thermosetting composition for optical semiconductors of the present invention has a moderate flexibility. In other words, the crack resistance is extremely excellent.
The bifunctional silicone resin has an average composition formula represented by the following general formulas (16) to (19). The thermosetting composition for optical semiconductors of the present invention has the following general formula ( In the case of containing only the resin components represented by 16) to (19), but in the case of a mixture containing resin components having various structures, the following general formula It also means the case represented by (16) to (19).

In the general formula (16), R ³⁹ and / or R ⁴⁰ is a glycidyl-containing group, and R ³⁷ and R ^{38 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. When only one of R ^{39 and} R ⁴⁰ is a glycidyl-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit for r / (r + s) is 0.6, the preferred upper limit is 0.95, the more preferred lower limit is 0.7, the more preferred upper limit is 0.9, and the preferred lower limit for s / (r + s) is 0. 0.05, a preferred upper limit is 0.4, a more preferred lower limit is 0.1, and a more preferred upper limit is 0.3.

In the general formula (17), R ⁴⁵ and / or R ⁴⁶ is a glycidyl-containing group, and R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ are linear or branched hydrocarbons having 1 to 8 carbon atoms. Or the fluoride is represented, and these may be the same as each other or different. When only one of R ^{45 and} R ⁴⁶ is a glycidyl-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit of t + u / (t + u + v) is 0.6, the preferred upper limit is 0.95, the more preferred lower limit is 0.7, the more preferred upper limit is 0.9, and the preferred lower limit of v / (t + u + v) is 0. 0.05, a preferred upper limit is 0.4, a more preferred lower limit is 0.1, and a more preferred upper limit is 0.3.

In the general formula (18), R ⁴⁹ , R ⁵⁰ and / or R ⁵¹ are glycidyl-containing groups, and R ⁴⁷ and R ⁴⁸ are linear or branched hydrocarbons having 1 to 8 carbon atoms or fluorine thereof. Which may be the same or different from each other. In addition, when any of R ⁴⁹ , R ⁵⁰ or R ⁵¹ is a glycidyl-containing group and any of them is not a glycidyl-containing group, a group that is not a glycidyl-containing group is a linear or branched carbon having 1 to 8 carbon atoms. Represents a hydrocarbon or its fluoride. The preferred lower limit of w / (w + x) is 0.70, the preferred upper limit is 0.999, the more preferred lower limit is 0.8, the more preferred upper limit is 0.995, and the preferred lower limit for q / (p + q) is 0. 0.001, a preferred upper limit is 0.3, a more preferred lower limit is 0.005, and a more preferred upper limit is 0.2.

In General Formula (19), R ⁵⁶ , R ⁵⁷ and / or R ⁵⁸ are glycidyl-containing groups, and R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are linear or branched carbon atoms having 1 to 8 carbon atoms. Or a fluorinated product thereof may be the same as or different from each other. Further, when any of R ⁵⁶ , R ⁵⁷ or R ⁵⁸ is a glycidyl-containing group and any of them is not a glycidyl-containing group, a non-glycidyl-containing group is a linear or branched C 1-8. Represents a hydrocarbon or its fluoride. The preferable lower limit of (y + z) / (y + z + A) is 0.70, the preferable upper limit is 0.999, the more preferable lower limit is 0.8, and the more preferable upper limit is 0.995, and the preferable lower limit of A / (y + z + A). Is 0.001, a preferable upper limit is 0.3, a more preferable lower limit is 0.005, and a more preferable upper limit is 0.2.

In the bifunctional silicone resin (B), the bifunctional structural unit has a structure represented by the following general formula (3-2), that is, one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit is a hydroxyl group. Or the structure which comprises an alkoxy group is included.
(R ¹ R ² SiXO _1/2 ) (3-2)
In the general formula (3-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the general formula (3-2), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, An isopropoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, etc. are mentioned.

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

The method for synthesizing such a bifunctional silicone resin is not particularly limited, and examples thereof include the same method as the method for synthesizing the silicone resin.
In addition, such a bifunctional silicone resin synthesizes a desired silicone resin having a number average molecular weight (Mn) and a molecular weight of about 5000 to 30,000, and then condenses an alkoxysilane compound having a glycidyl ether group-containing group with a catalyst. Can also be synthesized. According to such a synthesis method, it is easy to adjust the silicone chain length between glycidyl ether groups to a desired length by adjusting the molecular weight of the silicone resin and the amount of the alkoxysilane compound to be added, which is preferable.
In addition, the silicone chain length between glycidyl ether groups means the length of the resin part by repeating only the silicone block which does not have a glycidyl group, and it is preferable that it becomes about 1500-15000 in number average molecular weight (Mn).

The blending amount of the bifunctional silicone resin is not particularly limited, but the preferred lower limit is 10 parts by weight and the preferred upper limit is 120 parts by weight with respect to 100 parts by weight of the silicone resin. When the amount is less than 10 parts by weight, the blending effect may not be sufficiently obtained. When the amount exceeds 120 parts by weight, the heat resistance of the resulting cured product of the thermosetting composition for optical semiconductors is inferior, and the cured product is It may become yellowing easily in a thermal environment. A more preferred lower limit is 15 parts by weight, and a more preferred upper limit is 100 parts by weight.

The thermosetting composition for optical semiconductors of this invention contains the thermosetting agent which can react with the said cyclic ether containing group.
The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group of the silicone resin. For example, ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylamino Aromatic amines such as piperazine and isophoronediamine, metaphenylenediamine, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenolmethane, 4,4′-diaminodiphenol ether Phenols such as amines, mercaptopropionic acid esters, mercaptans such as terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak Resins; polyols obtained by hydrogenating aromatic rings of these phenolic resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene- 2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, cyclohexane- Alicyclic acid anhydrides such as 1,2,3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, 3-methylglutaric acid anhydride, etc. 3-alkylglutaric anhydride, 2-ethyl-3-propiyl having 1 to 8 carbon atoms which may be branched 2,3-dialkyl glutaric anhydride, 2,4-diethyl glutaric anhydride, 2,4-dimethyl glutaric anhydride having an optionally branched alkyl group having 1 to 8 carbon atoms such as glutaric anhydride Alkyl-substituted glutaric anhydrides such as 2,4-dialkylglutaric anhydrides having a C 1-8 alkyl group which may be branched such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Aromatic acid anhydrides such as acids, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and salts thereof, the above aliphatic amines, aromatic amines, and / or Amine adducts obtained by reaction of imidazoles with epoxy resins, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1 , 8-diazabicyclo [5.4.0] undecene-7, tertiary amines such as triphenylphosphine, dicyandiamide, and the like. Among these, acid anhydrides such as alicyclic acid anhydrides, alkyl-substituted glutaric acid anhydrides, and aromatic acid anhydrides are preferable, and alicyclic acid anhydrides and alkyl-substituted glutaric acid anhydrides are more preferable. And particularly preferably methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, cyclohexane-1,2. , 3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, 2,4-diethylglutaric anhydride. These thermosetting agents may be used independently and 2 or more types may be used together. In addition, when it contains the bifunctional silicone resin mentioned above, these thermosetting agents can also react with the glycidyl containing group of this bifunctional silicone resin.

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

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

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

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

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

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

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

The 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.

By using the thermosetting composition for optical semiconductor elements of the present invention, an encapsulant for optical semiconductor elements can be produced. The encapsulant for optical semiconductor elements thus obtained is also one aspect of the present invention.

By using the thermosetting composition for optical semiconductor elements of the present invention, the method for producing an encapsulant for optical semiconductor elements is not particularly limited. For example, the light of the present invention is inserted into a mold frame in which a light emitting element is inserted. Examples thereof include a method of injecting a semiconductor sealing agent and curing.

By using the encapsulant for optical semiconductor elements of the present invention, an optical semiconductor device can be produced. That is, by the optical semiconductor element sealing agent of the present invention, an electrode portion comprising electrodes formed on the optical semiconductor element package material, and an optical semiconductor connected to the electrode portion on the optical semiconductor element package material By sealing the element, an optical semiconductor element package material, an electrode portion formed of an electrode formed on the optical semiconductor element package material, an optical semiconductor element connected to the electrode portion, An optical semiconductor device comprising an optical semiconductor element sealing agent that seals the electrode portion and the optical semiconductor element can be produced.

FIG. 1 is a top view schematically showing an optical semiconductor device using the encapsulant for optical semiconductor elements of the present invention. FIG. 2 is a cross-sectional view schematically showing an optical semiconductor device using the encapsulant for optical semiconductor elements of the present invention. 1 and 2, 1 is an optical semiconductor device, 2 is an optical semiconductor element package material, 21 is an exposed portion of the optical semiconductor element package material, 3 is an electrode portion, 4 is an optical semiconductor element, and 5 is a wire. . As shown in FIG. 1, in the optical semiconductor device 1, an electrode part 3 is formed on a package material 2 for an optical semiconductor element, and the optical semiconductor element 4 is connected to the electrode part 3 by a wire 5. In the optical semiconductor element 1, the electrode portion 3, the optical semiconductor element 4, and the wire 5 are sealed with the optical semiconductor element sealing agent of the present invention.

In the optical semiconductor device, when the entire area of the electrode portion is S1 and the exposed area of the exposed portion of the optical semiconductor element package material is S2, the preferable lower limit of the value of S1 / S2 is 0.5, and the preferable upper limit. Is 20. If it is less than 0.5, an optical semiconductor device having a large package area may not be obtained, and reflection efficiency may deteriorate. If it exceeds 20, peeling may occur between the package material for optical semiconductor elements and the electrode part, or a short circuit between the electrodes may occur.
FIG. 3 is a top view of an optical semiconductor device using the encapsulant for optical semiconductor elements of the present invention, and shows an overall area S1 of the electrode part 3 and an exposed area S2 of the exposed part 21 of the optical semiconductor element package material. FIG. As shown in FIG. 3, in the present specification, the exposed portion of the optical semiconductor element package material is, for example, an electrode portion is not formed on the bottom surface of the optical semiconductor element package material having a concave shape, and the optical semiconductor element. The part where the packaging material is exposed.

Thus, an optical semiconductor element package material, an electrode portion formed of an electrode formed on the optical semiconductor element package material, and an optical semiconductor element connected to the electrode on the optical semiconductor element package material, An optical semiconductor device in which the electrode part and the optical semiconductor element are sealed with the optical semiconductor element sealing agent of the present invention on the optical semiconductor element package material, and the entire area S1 of the electrode part An optical semiconductor device in which the exposed area S2 of the exposed portion of the optical semiconductor element package material satisfies the relationship of S1 / S2 = 0.5 to 20 is also one aspect of the present invention.

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, and the heat resistance and light resistance are excellent, and the adhesiveness to the housing material and the metal electrode material is excellent. The thermosetting composition for optical semiconductors which can prevent generation | occurrence | production of the crack of this, the sealing agent for optical semiconductor elements, and an optical semiconductor device 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 (440 g) and 3-glycidoxypropyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise thereto, and after the addition was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer A. The molecular weight of the polymer A is Mn = 2000, Mw = 3800, and (Me ₂ SiO _2/2 ) _0.83 (EpSiO _3/2 ) _0.17 from ²⁹ Si-NMR.
3-glycidoxypropyl group content is 22 mol%, epoxy equivalent is 550 g / e
q. Met.
The molecular weight was stirred until tetrahydrofuran (1 mL) was added and dissolved in polymer A (10 mg), and a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK) Measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene) were used for GPC measurement. Moreover, the epoxy equivalent was calculated | required based on JISK-7236.

(Synthesis Example 2)
Dimethyldimethoxysilane (440 g) and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise thereto, and after the addition was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer B. The molecular weight of the polymer B is Mn = 2300, Mw = 4800, and (Me ₂ SiO _2/2 ) _0.84 (EpSiO _3/2 ) _0.16 from ²⁹ Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 22 mol%, and the epoxy equivalent was 550 g / eq. Met.
The molecular weight, epoxy equivalent, and alkoxy content of polymer B were determined in the same manner as in Synthesis Example 1.

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

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

(Example 1)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R8200 (fine powder silica [trimethylsilyl Treatment, specific surface area: 160 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 20 g), 3-mercaptopropyltrimethoxysilane (0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. . This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 2)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R8200 (fine powder silica [trimethylsilyl Treatment, specific surface area: 160 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 20 g), 3-mercaptopropyltrimethoxysilane (0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. . This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 3)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R8200 (fine powder silica [trimethylsilyl Treatment, specific surface area: 160 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 20 g), 3-trimethoxysilylpropyl succinic acid (0.5 g), mixed and degassed to obtain an encapsulant for optical semiconductor elements. It was. 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 4
Polymer C (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 20 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R8200 (fine powder silica [trimethylsilyl Treatment, specific surface area: 160 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 20 g), 3-mercaptopropyltrimethoxysilane (0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. . This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 5)
Polymer D (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 20 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), AEROSIL R8200 (fine powder silica [trimethylsilyl Treatment, specific surface area: 160 m ² / g], manufactured by Nippon Aerosil Co., Ltd., 20 g), 3-mercaptopropyltrimethoxysilane (0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. . This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 1)
An optical semiconductor encapsulant and a cured product were prepared in the same manner as in Example 1 except that 3-mercaptopropyltrimethoxysilane (0.5 g) was not used.

(Comparative Example 2)
A sealed optical semiconductor and a cured product were produced in the same manner as in Example 2 except that 3-mercaptopropyltrimethoxysilane (0.5 g) was not used.

(Comparative Example 3)
Except that 3-mercaptopropyltrimethoxysilane (0.5 g) was used, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane (0.5 g) was used, the same procedure as in Example 2 was repeated. A semiconductor encapsulant and a cured product were prepared.

(Comparative Example 4)
Encapsulation for optical semiconductors in the same manner as in Example 2, except that 3-glucidoxypropyltrimethoxysilane (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g). An agent and a cured product were prepared.

(Comparative Example 5)
For optical semiconductors as in Example 2, except that 3-glucidoxypropyl (methyl) dimethoxysilane (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g) A sealant and a cured product were prepared.

(Comparative Example 6)
Sealant for optical semiconductor in the same manner as in Example 2 except that 3-methacryloxypropyltrimethoxysilane (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g). And a cured product was prepared.

(Comparative Example 7)
A sealing compound for optical semiconductors and a sealing compound for optical semiconductors in the same manner as in Example 2 except that 3-aminopropyltriethoxysilane (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g). A cured product was produced.

(Comparative Example 8)
For optical semiconductors in the same manner as in Example 2 except that N-phenyl-3-aminopropyltrimethoxysilane (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g). A sealant and a cured product were prepared.

(Comparative Example 9)
Example except that 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g) In the same manner as in No. 2, an optical semiconductor encapsulant and a cured product were produced.

(Comparative Example 10)
Example 2 was repeated except that N-methyl [3- (trimethoxysilyl) -propyl] carbamate (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g). Thus, an optical semiconductor encapsulant and a cured product were prepared.

(Comparative Example 11)
The sealing compound for optical semiconductors and the sealing agent for optical semiconductors in the same manner as in Example 2 except that 3-ureidopropyltriethoxysilane (0.5 g) was used instead of 3-mercaptopropyltrimethoxysilane (0.5 g). A cured product was produced.

(Evaluation)
The following evaluation was performed about the sealing agent for optical semiconductors and hardened | cured material which were obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(1) Initial light transmittance The light transmittance of 400 nm was measured using "U-4000" made 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 Tables 1 and 2, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ less than 10%: ○, less than 10-40%: △, 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 Tables 1 and 2, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ less than 10%: ○, less than 10-40%: △, 40% or more : X.

(Preparation of die bond material for optical semiconductor elements)
A flaky silver powder (170 g) having an average particle size of 3 μm and a maximum particle size of 20 μm was added to polymer B (30 g), and the mixture was stirred and kneaded using three rolls.
The flaky silver powder-containing polymer (100 g) was added with Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 3.75 g), U-CAT SA 102 (manufactured by Sun Apro, 0.075 g), 3-mercaptopropyl. Trimethoxysilane (0.075 g) was added and mixed and degassed to obtain a die bond material for optical semiconductor elements.

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

(4) Moisture absorption high temperature adhesion test The produced optical semiconductor elements (20 pieces) were allowed to stand at 85 ° C. and 85 RH% for 24 hours, and the absorbed optical semiconductor elements were placed in an oven at 200 ° C. to give a rapid heat change, The peeling from the housing material and the metal electrode was confirmed.

(5) Moisture absorption reflow test and cooling cycle test The produced optical semiconductor elements (20 pieces) were allowed to stand at 85 ° C. and 85 RH% for 24 hours, and the absorbed optical semiconductor elements were solder reflow oven (preheat 150 ° C. × 100 seconds + reflow). [Maximum temperature 260 ° C.]) The number of cracks after passing three times, the number of peeling from the housing material and the metal electrode was confirmed (moisture absorption reflow test).
Further, the optical semiconductor elements (20 pieces) subjected to the moisture absorption reflow test were subjected to 500 cycles of a cooling cycle at −60 ° C. for 30 minutes and 140 ° C. for 30 minutes to confirm the number of cracks and peeling from the housing material (cooling cycle). test).

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, and the heat resistance and light resistance are excellent, and the adhesiveness to the housing material and the metal electrode material is excellent. The thermosetting composition for optical semiconductors which can prevent generation | occurrence | production of the crack of this, the sealing agent for optical semiconductor elements, and an optical semiconductor device can be provided.

It is a top view which shows typically the optical semiconductor device which uses the sealing compound for optical semiconductor elements of this invention. It is sectional drawing which shows typically the optical semiconductor device formed using the sealing agent for optical semiconductor elements of this invention. In the top view of the optical semiconductor device using the sealing agent for optical semiconductor elements of this invention, it is a schematic diagram which shows the whole area S1 of an electrode part, and the exposed area S2 of the exposed part of the package material for optical semiconductor elements. is there.

Claims (4)

A silicone resin having a cyclic ether-containing group, a thermosetting agent capable of reacting with the cyclic ether-containing group, a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2): A thermosetting composition for optical semiconductors comprising:
The silicone resin is composed mainly of a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4), and when the total number of structural units included is 1, The content of the structural unit represented by the general formula (3) is 0.6 to 0.95 (mol conversion), and the content of the structural unit represented by the general formula (4) is 0.05 to 0.4. The thermosetting composition for optical semiconductors is (molar conversion) and the content of the cyclic ether-containing group is 5 to 40 mol%.

In General Formula (1), R ^a represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ^b represents a hydrocarbon group having 1 to 8 carbon atoms, and R ^c represents 1 to 1 carbon atoms. 5 represents an alkyl group, and n represents 1 to 3.

In the general formula (3) and ^(4), R 1, ^{R 2} and ^{R 3} is at least one represents a cyclic ether-containing group, ^R 1, ^{R 2} and ^{R 3} other than the cyclic ether-containing group, the carbon Represents a hydrocarbon of formula 1 to 8 or a fluorinated product thereof, which may be the same or different from each other, and furthermore, in the repeating structure in the silicone resin skeleton, a plurality of different types of R ¹ , R ² and R ³ may be contained. Furthermore, the bifunctional silicone resin which has 1 or more of glycidyl containing groups in a molecule | numerator is contained, The thermosetting composition for optical semiconductors of Claim 1 characterized by the above-mentioned. An encapsulant for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1 or 2. An optical semiconductor element package material, an electrode portion formed of an electrode formed on the optical semiconductor element package material, and an optical semiconductor element connected to the electrode on the optical semiconductor element package material, An optical semiconductor device in which the electrode portion and the optical semiconductor element are sealed with the optical semiconductor element sealing agent according to claim 3 on the optical semiconductor element package material,
An optical semiconductor device characterized in that the overall area S1 of the electrode portion and the exposed area S2 of the exposed portion of the optical semiconductor element packaging material satisfy a relationship of S1 / S2 = 0.5-20.

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