JP5660145B2 - Curable composition, cured product, and optical semiconductor device - Google Patents

Description

  The present invention relates to a curable composition, a cured product, and an optical semiconductor device.

  Silicone resins have been widely used as sealing materials for semiconductor elements including LED elements. Silicone resin is superior in heat resistance, transparency, and discoloration resistance compared to epoxy resin that has been used as a conventional sealing material, but it has low mechanical properties such as bending strength. There is a problem that cracks are likely to occur due to a thermal shock or a high temperature and high humidity environment.

As a technique for preventing the occurrence of such cracks, Patent Document 1 discloses a branched organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule and having a specific siloxane unit, and one molecule. An organopolysiloxane composition comprising a linear organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms and having a viscosity at 25 ° C. of 1000 mPa · s or less, and an addition reaction catalyst Is disclosed. Patent Document 2 discloses an alkenyl group-containing polyorganosiloxane composed of a linear polyorganosiloxane having a specific organic group and a branched polyorganosiloxane having a specific siloxane unit, and 3 in a molecule having a specific siloxane unit. A polyorganosiloxane composition containing a polyalkylhydrogensiloxane containing one or more silicon-bonded hydrogen atoms and a platinum group metal compound is disclosed.

JP 2011-225715 A JP 2006-335857 A

  An object of this invention is to provide the curable polysiloxane composition which can form the hardened | cured material which has high tolerance with respect to a thermal shock, high temperature, high humidity conditions, etc., and is hard to produce a crack also in a severe environment.

  The present invention comprises a curable composition comprising a compound (A) represented by the following formula (1), a polysiloxane (B) represented by the following chemical formula (2), and a hydrosilylation catalyst (C). It is.

（式中、ｎは１以上の整数を示す。Ｒ¹およびＲ²は炭素数１〜４のアルキル基を示す。Ａｒはアリール基を示す。）

(In the formula, n represents an integer of 1 or more. R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms. Ar represents an aryl group.)

（式中、Ｒ³、Ｒ⁵およびＲ⁶はそれぞれ独立に有機基を示す。ただし、すべてのＲ³およびＲ⁶のうちの少なくとも２つはアルケニル基であり、Ｒ⁵は、そのＲ⁵が結合するケイ素原子に結合するもう１つのＲ⁵がアリール基であるとき、炭素数１〜４のアルキル基およびアリール基ではない。Ｒ⁴はそれぞれ独立に炭素数１〜４のアルキル基またはアリール基を示し、Ｒ⁴のうち少なくとも１つはアリール基を示す。Ｘは水素原子または炭素数１〜３のアルキル基を示す。ａ、ｃ、ｅおよびｆはそれぞれ独立に０以上の整数を示す。ｂおよびｄはそれぞれ独立に１以上の整数を示す。ただし、ａが０であるとき、ｄは２以上の整数である。）

(Wherein, shows the R ^3, R ⁵ and R ⁶ each independently represents an organic group. However, at least two of all R ³ and R ⁶ is an alkenyl group, R ⁵ is, its R ⁵ When another R ⁵ bonded to the bonding silicon atom is an aryl group, it is not an alkyl group or aryl group having 1 to 4 carbon atoms, and R ⁴ is independently an alkyl group or aryl group having 1 to 4 carbon atoms. And at least one of R ⁴ represents an aryl group, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a, c, e and f each independently represents an integer of 0 or more. b and d each independently represent an integer of 1 or more, provided that when a is 0, d is an integer of 2 or more.)

In the curable composition, R ^{4 in the} chemical formula (2) is preferably an aryl group.
Another invention is a cured product obtained by curing the curable composition.
Another invention is an optical semiconductor device having the cured product.

The curable composition of the present invention has high resistance to thermal shock, high temperature and high humidity conditions, and can form a cured product that is less prone to crack even in harsh environments.
Therefore, an optical semiconductor device obtained by coating a semiconductor light emitting element with a cured product obtained from this curable composition is an optical semiconductor device with excellent reliability.

FIG. 1 is a schematic diagram showing a specific example of an optical semiconductor device.

<Curable composition>
The curable composition of the present invention contains a compound (A) represented by the following formula (1), a polysiloxane (B) represented by the following chemical formula (2), and a hydrosilylation reaction catalyst (C).

（式中、ｎは１以上の整数を示す。Ｒ¹およびＲ²は炭素数１〜４のアルキル基を示す。Ａｒはアリール基を示す。）

(In the formula, n represents an integer of 1 or more. R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms. Ar represents an aryl group.)

（式中、Ｒ³、Ｒ⁵およびＲ⁶はそれぞれ独立に有機基を示す。ただし、すべてのＲ³およびＲ⁶のうちの少なくとも２つはアルケニル基であり、Ｒ⁵は、そのＲ⁵が結合するケイ素原子に結合するもう１つのＲ⁵がアリール基であるとき、炭素数１〜４のアルキル基およびアリール基ではない。Ｒ⁴はそれぞれ独立に炭素数１〜４のアルキル基またはアリール基を示し、Ｒ⁴のうち少なくとも１つはアリール基を示す。Ｘは水素原子または炭素数１〜３のアルキル基を示す。ａ、ｃ、ｅおよびｆはそれぞれ独立に０以上の整数を示す。ｂおよびｄはそれぞれ独立に１以上の整数を示す。ただし、ａが０であるとき、ｄは２以上の整数である。）
なお、本発明において「ポリシロキサン」とは、シロキサン単位 (Ｓｉ−Ｏ)が２個以上結合した分子骨格を有するシロキサンを意味する。

(Wherein, shows the R ^3, R ⁵ and R ⁶ each independently represents an organic group. However, at least two of all R ³ and R ⁶ is an alkenyl group, R ⁵ is, its R ⁵ When another R ⁵ bonded to the bonding silicon atom is an aryl group, it is not an alkyl group or aryl group having 1 to 4 carbon atoms, and R ⁴ is independently an alkyl group or aryl group having 1 to 4 carbon atoms. And at least one of R ⁴ represents an aryl group, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a, c, e and f each independently represents an integer of 0 or more. b and d each independently represent an integer of 1 or more, provided that when a is 0, d is an integer of 2 or more.)
In the present invention, “polysiloxane” means a siloxane having a molecular skeleton in which two or more siloxane units (Si—O) are bonded.

Compound (A)
Compound (A) is a compound represented by the above formula (1). The compound (A) is a linear polysiloxane and has two silicon-bonded hydrogen atoms per molecule. Silicon-bonded hydrogen atoms are present in the siloxane units at both ends of the molecule. Compound (A) is a crosslinking agent for polysiloxane (B) and forms a cured product by a hydrosilylation reaction with polysiloxane (B).

R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms. That is, the compound (A) is a hydrogen siloxane having one or more D unit siloxane units in which an aryl group and an alkyl group having 1 to 4 carbon atoms are bonded to a silicon atom. Such a compound (A) having a D unit siloxane unit is a hydrogen siloxane containing a D unit siloxane unit having two aryl groups, or a hydrogen siloxane containing a D unit siloxane unit having two alkyl groups. Compared with Gensiloxane, the crystallinity is lowered. For this reason, the hardened | cured material obtained from the curable composition obtained by using together a compound (A) and the following polysiloxane (B) becomes a flexible structure partially, and has high tolerance with respect to a thermal shock etc. And cracks are less likely to occur.

The alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, etc. isobutyl and tert- butyl group, these inter alia A methyl group is preferred.

  Examples of the aryl group include aromatic hydrocarbon groups such as phenyl group and tolyl group, and heteroaryl groups such as thienyl group and pyridyl. Moreover, the group formed by substituting the hydrogen atom of groups, such as the phenyl group mentioned above, by groups, such as a halogen atom and an alkyl group, may be sufficient. When n in the formula (1) is an integer of 2 or more, the n Ars present in the formula (1) may be the same kind of aryl groups or different kinds of aryl groups.

In said formula (1), n shows an integer greater than or equal to 1, Preferably it is an integer of 1-3.
Compound (A), for example, can be obtained by reacting any and alkoxysilanes methylphenyl dimethoxy Sila down, by a known method and hydrogen siloxane such as 1,1,3,3-tetramethyldisiloxane .

  The content of the compound (A) in the curable composition of the present invention is such that the molar ratio of the amount of silicon atom-bonded hydrogen atoms in the compound (A) to the amount of alkenyl groups in the polysiloxane (B) is 0.1 to 5. The amount is preferably 0.5 to 2, more preferably 0.7 to 1.4. When the content of the compound (A) is within the above range, a cured product that has high resistance to thermal shock and the like and hardly causes cracks is easily formed, and curing of the composition proceeds sufficiently.

Polysiloxane (B)
The polysiloxane (B) is a polysiloxane represented by the above formula (2). The polysiloxane (B) is a main component of the composition, and is cured by a hydrosilylation reaction with the compound (A) to become a main component of the cured product.

In said formula (2), R < ³ >, R < ⁵ > and R < ⁶ > show an organic group each independently. Three R ³ contained in one siloxane unit may be different organic groups, two may be the same organic group, the other one may be a different organic group, and all three may be the same It may be an organic group. When a is an integer of 2 or more, the plurality of siloxane units containing R ³ may be the same or different from each other, some of the plurality are the same, It may be different. Two R ^{5 s} contained in one siloxane unit may be different organic groups or the same organic group. When c is an integer of 2 or more, the plurality of siloxane units including R ⁵ may be the same or different from each other, some of the plurality are the same, It may be different. When d is an integer of 2 or more, the plurality of siloxane units containing R ⁶ may be the same or different from each other, some of the plurality are the same, and others are the same. May be different.

Examples of the organic group include an alkyl group, an alkenyl group, and an aryl group.
The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group. Among these, a methyl group is preferable.

  Examples of the alkenyl group include a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, heptenyl group, hexenyl group, and cyclohexenyl group. Among these, a vinyl group, an allyl group, and a hexenyl group are preferable.

As an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned, for example, Among these, a phenyl group is preferable.
The organic group may be a group including an epoxy group. When the polysiloxane (B) has a group containing an epoxy group as an organic group, it hardly inhibits the hydrosilylation reaction that occurs when the curable composition is cured, and forms a cured product having high adhesion to a substrate or a metal wiring. can do. Examples of the group having an epoxy group include glycidoxyalkyl groups such as glycidoxy group and 3-glycidoxypropyl group, 3,4-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 2- (3 , 4-epoxycyclopentyl) ethyl group, and epoxycycloalkyl groups such as 2- (3,4-epoxycyclohexyl) ethyl group.

However, at least two of all R ³ and R ⁶ contained in one molecule are alkenyl groups, and preferably 2 to 4 are alkenyl groups. That is, polysiloxane (B) has two or more alkenyl groups per molecule. Two or more of R ³ may be alkenyl groups, R ⁶ may be all groups other than alkenyl groups, R ³ may be all groups other than alkenyl groups, and two or more of R ⁶ are alkenyl groups A group, one or more of R ³ may be an alkenyl group , and one or more of R ⁶ may be an alkenyl group.

Further, R ⁵ may then another R ⁵ bonded to the silicon atoms of R ⁵ are attached is an aryl group, not alkyl groups and aryl groups of 1 to 4 carbon atoms. That is, the siloxane unit containing R ⁵ is not the same as the siloxane unit containing R ⁴ .

In the above formula (2), two R ⁴ contained in one siloxane unit each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and at least one of R ⁴ represents an aryl group. When b is an integer of 2 or more, the plurality of siloxane units containing R ⁴ may be the same or different from each other, some of the plurality are the same, and others are the same. May be different. That is, the polysiloxane (B) has at least one D unit in which an aryl group and an alkyl group having 1 to 4 carbon atoms are bonded to a silicon atom as a siloxane unit containing R ⁴ , Have only one or more D units to which an aryl group is bonded, or one or more D units to which an aryl group and an alkyl group having 1 to 4 carbon atoms are bonded to a silicon atom, and two aryl groups to the silicon atom Have one or more D units bonded to each other. Curing that can form a cured product that has high resistance to thermal shock and hardly cracks by using the polysiloxane (B) having a siloxane unit of D unit and the compound (A) in combination. It becomes possible to obtain a sex composition.

Further, if R ⁴ is an aryl group, that is, if the polysiloxane (B) has only a D unit in which two aryl groups are bonded to a silicon atom as a siloxane unit containing R ⁴ , cracks are unlikely to occur, Furthermore, it is preferable at the point which can form hardened | cured material with high gas barrier property with respect to water vapor | steam.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl group. Of these, a methyl group is particularly preferred.

Examples of the aryl group R ⁴ represents a phenyl group, a tolyl group, a xylyl group, a naphthyl group, these inter alia Fe two Le group.
X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  a, c, e and f each independently represent an integer of 0 or more. b and d each independently represent an integer of 1 or more. However, when a is 0, d is an integer of 2 or more. Since d is an integer of 1 or more, the polysiloxane (B) has a T unit siloxane unit and therefore has a branched structure. Even if a composition is prepared by using a polysiloxane having no branched structure and the compound (A) in combination, the composition is hardly cured. Further, even when the composition is cured, the obtained cured product does not have crack resistance.

  a is preferably 0 to 5, more preferably 1 to 3. b is preferably 1 to 5, more preferably 1 to 3. c is preferably 0 to 3, more preferably 0 to 1. d is preferably 1 to 9, more preferably 4 to 7. e is preferably 0 to 5, more preferably 0 to 1.

  The content of the polysiloxane (B) contained in the curable composition of the present invention is 100% by mass of the total of the component (A), the component (B) and the component (C) contained in the composition. When it is, it is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and further preferably 50 to 80% by mass. When the content of the polysiloxane (B) is within the above range, a cured product having high resistance to thermal shock and the like, which hardly causes cracks, is easily formed, and curing of the composition proceeds sufficiently. .

  Polysiloxane (B) preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 100 to 50000, and more preferably in the range of 500 to 5000. Details of measurement conditions by gel permeation chromatography are as described in Examples. When the weight average molecular weight of the polysiloxane (B) is within the above range, it is easy to handle when producing a sealing material using the composition, and the cured product obtained from the composition is used as an optical semiconductor sealing material. Has sufficient material strength and properties.

  As a method for producing the polysiloxane (B), JP-A-6-9659, JP-A-2003-183582, JP-A-2007-008996, JP-A-2007-106798, JP-A-2007-169427. And known methods described in JP 2010-059359 A, for example, a method of co-hydrolyzing chlorosilane and alkoxysilane serving as each unit source, and an equilibration reaction of the co-hydrolyzed product with an alkali metal catalyst or the like. The method etc. are mentioned.

Catalyst for hydrosilylation reaction (C)
The hydrosilylation catalyst (C) is a catalyst for hydrosilylation reaction between the compound (A) and the polysiloxane (B).

  The hydrosilylation reaction catalyst (C) can be used without any particular limitation as long as it is a catalyst used as a hydrosilylation reaction catalyst in a conventional hydrosilyl polysiloxane composition.

Specific examples of the hydrosilylation catalyst (C) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Among these, a platinum-based catalyst is preferable from the viewpoint of promoting the curing of the present composition. Examples of the platinum-based catalyst include a platinum-alkenylsiloxane complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Etc. In particular, from the viewpoint of stability of the complex, 1,3-divinyl-1,1,3,3-tetra- disiloxane is preferable.

The content of the hydrosilylation reaction catalyst (C) in the curable composition of the present invention is such that the hydrosilylation reaction between the compound (A) and the polysiloxane (B) can actually proceed.
As long as the object of the present invention is achieved, the curable composition of the present invention can contain, for example, fumed silica, fine particle silica such as quartz powder, titanium oxide, zinc oxide, etc. Inorganic filler, retarder such as cyclo-tetramethyltetravinyltetrasiloxane, diluent such as diphenylbis (dimethylvinylsiloxy) silane, phenyltris (dimethylvinylsiloxy) silane, phosphor, pigment, flame retardant, heat-resistant agent Further, an antioxidant and the like can be contained.

The curable composition of this invention can be prepared by mixing each said component uniformly by well-known methods, such as a mixer.
As a viscosity in 25 degreeC of the curable composition of this invention, Preferably it is 1-1000000 mPa * s, More preferably, it is 10-10000 mPa * s. When the viscosity is within this range, the operability of the composition is improved.

  The curable composition of the present invention can be prepared as one liquid, or can be prepared by dividing into two liquids, and the two liquids can be mixed and used at the time of use. If necessary, a small amount of a curing inhibitor such as acetylene alcohol may be added.

<Hardened product>
A cured product is obtained by curing the curable composition of the present invention. If a semiconductor element is sealed with the curable composition of the present invention and cured, a cured product as a sealing material is obtained.

Examples of the method for curing the curable composition of the present invention include a method in which the curable composition is applied on a substrate and then heated at 100 to 180 ° C. for 1 to 13 hours.
As described above, the cured product obtained by curing the curable composition of the present invention has high resistance to thermal shock and the like, and is less likely to crack even in a harsh environment.

<Optical semiconductor device>
The optical semiconductor device of the present invention has a cured product obtained by curing the curable composition. For example, the optical semiconductor device of the present invention includes a semiconductor light emitting element and the cured product that covers the semiconductor light emitting element. The optical semiconductor device of the present invention is obtained by coating a semiconductor light emitting element with the curable composition and curing the composition. The method for curing the curable composition is as described above.
Examples of the optical semiconductor device include an LED (Light Emitting Diode) and an LD (Laser Diode).

FIG. 1 is a schematic view of a specific example of the optical semiconductor device of the present invention. The optical semiconductor device 1 is disposed so as to accommodate an electrode 6 such as a silver electrode, a semiconductor light emitting element 2 installed on the electrode 6 and electrically connected to the electrode 6 by a wire 7, and the semiconductor light emitting element 2. And the sealing material 4 which is filled in the reflector 3 and seals the semiconductor light emitting element 2. The sealing material 4 consists of hardened | cured material obtained by hardening the curable composition of this invention. In the sealing material 4, particles 5 such as silica and phosphor are dispersed.

  As described above, the cured product obtained by curing the curable composition of the present invention is less susceptible to cracking even under harsh environments, so the optical semiconductor device having the cured product as a sealing material is subject to thermal shock. It can be used under low temperature and high temperature and high humidity conditions.

1. Preparation of curable composition
1-1. Structural analysis The structure of the synthesized compound was calculated by ²⁹ Si NMR and ¹³ C NMR.
1-2. Weight average molecular weight Weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions and was determined as a polystyrene equivalent value.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore HXL-M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL

1-3. Synthesis of each component The following siloxane units are indicated by the following symbols.
M (Vi): (ViMe ₂ SiO _1/2 )
D (MePh) :( MePhSiO _2/2 )
D (MeEp) :( MeEpSiO _2/2 )
D (Ph) :( Ph ₂ SiO _2/2 )
T (Ph) :( PhSiO _3/2 )
(Me represents a methyl group, Ph represents a phenyl group, Vi represents a vinyl group, and Ep represents an epoxy 3-glycidoxypropyl group.)

[Synthesis Example 1] Synthesis of Compound (A1) 455 g of methylphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, 336 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction kettle, and then 180 g of acetic acid was added. Then, it was made to react at 50 degreeC for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain a compound (A1) shown below.

[Synthesis Example 2] Synthesis of Compound (A2) 300 g of methylphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, 450 g of 1,1,3,3-tetramethyldisiloxane were added to a reaction kettle, and then 100 g of acetic acid was added. Then, it was made to react at 50 degreeC for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain a compound (A2) shown below.

[Synthesis Example 3] Synthesis of Compound (A3) 656 g of methylphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, 188 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction kettle, and then 280 g of acetic acid was added. Then, it was made to react at 50 degreeC for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain a compound (A3) shown below.

[Synthesis Example 4] Synthesis of Compound (D1) 403 g of diphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, 450 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction kettle, and then 130 g of acetic acid was added. And reacted at 50 ° C. for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain a compound (D1) shown below.

[Synthesis Example 5] Synthesis of Compound (D2) 403 g of diphenyldimethoxysilane, 40 g of dimethoxymethylsilane, 0.1 g of trifluoromethanesulfonic acid, 450 g of 1,1,3,3-tetramethyldisiloxane were placed in a reaction kettle, After adding 130 g of acetic acid, the mixture was reacted at 50 ° C. for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain a compound (D2) shown below.

[Synthesis Example 6] Synthesis of polysiloxane (B1) In a reaction kettle, 186 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 594 g of phenyltrimethoxysilane, 182 g of methylphenyldimethoxysilane, 180 g of water, The trifluoromethanesulfonic acid 0.8g and toluene 650g were put, and it heated and refluxed for 1 hour. Next, 1 g of 3-glycidoxypropylmethyldimethoxysilane and 0.6 g of potassium hydroxide were added and heated to reflux for 5 hours. After neutralizing with an acid, it was washed with water to obtain polysiloxane (B1) containing 60 mol of T (Ph), 20 mol of D (MePh) and 0.1 mol of D (MeEp) with respect to 20 mol of M (Vi). The weight average molecular weight of the polysiloxane (B1) was 1,400.

[Synthesis Example 7] Synthesis of polysiloxane (B2) In a reaction kettle, 186 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 595 g of phenyltrimethoxysilane, 244 g of diphenyldimethoxysilane, 200 g of water, trifluoro The solution was charged with 0.8 g of romethanesulfonic acid and 700 g of toluene and heated to reflux for 1 hour. Next, 0.6 g of potassium hydroxide was added and refluxed for 5 hours. After neutralizing with acetic acid, it was washed with water to obtain polysiloxane (B2) containing 60 mol of T (Ph) and 20 mol of D (Ph) with respect to 20 mol of M (Vi). The weight average molecular weight of the polysiloxane (B2) was 1,500.

[Synthesis Example 8] Synthesis of Compound (D3) 183 g of diphenyldimethoxysilane, 0.6 g of trifluoromethanesulfonic acid, and 140 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were placed in a reaction kettle. After adding 40 g of acetic acid, the mixture was reacted at 50 ° C. for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain a compound (D 3 ) shown below.

[Synthesis Example 9] Synthesis of polysiloxane (B3) In a reaction kettle, 149 g of phenyltrimethoxysilane, 183 g of diphenyldimethoxysilane, 0.6 g of trifluoromethanesulfonic acid, 1,3-divinyl-1,1,3,3-tetramethyl After adding 653 g of disiloxane and then adding 40 g of acetic acid, the mixture was reacted at 50 ° C. for 3 hours. After completion of the reaction, separation and extraction were performed using toluene and water to obtain polysiloxane (B3) containing 15 mol of T (Ph) and 15 mol of D (Ph) with respect to 70 mol of M (Vi). The weight average molecular weight of the polysiloxane (B3) was 500.

2. Preparation of curable composition [Examples 1 to 5 and Comparative Examples 1 to 3]
The components shown in Table 1 below were mixed in the blending amounts shown in Table 1 to obtain curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3. “Parts” in Table 1 indicates parts by mass. Note that the molar ratios of the amount of silicon-bonded hydrogen atoms in the compound (A) to the amount of alkenyl groups in the polysiloxane (B) are all 1.05. The details of each component in Table 1 are as follows.

ヒドロシリル化反応用触媒（Ｃ１）：白金と１，３−ジビニル−１，１，３，３−テトラメチルジシロキサンとの錯体(白金金属量４質量％)
化合物（Ｄ４）：シクロ−テトラメチルテトラビニルテトラシロキサン
化合物（Ｄ５）：ジフェニルビス（ジメチルビニルシロキシ）シラン
化合物（Ｄ６）：フェニルトリス（ジメチルビニルシロキシ）シラン

Hydrosilylation Kahan Applied catalyst (C1): complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum metal content 4% by weight)
Compound (D4): Cyclo-tetramethyltetravinyltetrasiloxane compound (D5): Diphenylbis (dimethylvinylsiloxy) silane compound (D6): Phenyltris (dimethylvinylsiloxy) silane

3. Evaluation of Curable Composition The curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated by the following methods (3-1) to ( 3-5 ). The evaluation results are shown in Table 2.
3-1. Heat resistance After the curable composition obtained in “2. Preparation of curable composition” was applied on quartz glass, it was heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours to form a film on the quartz glass. A cured product having a thickness of 1 mm was formed. The appearance before and after storing the cured product at 150 ° C. for 500 hours was visually observed to evaluate heat resistance. Evaluation was performed according to the following criteria.
A: No color change before and after storage.
B: Slightly yellow after storage.
C: The yellow color was clearly observed after storage.

3-2. Crack resistance after high-temperature and high-humidity test The curable composition obtained in “2. Preparation of curable composition” is injected into an LED package (surface-mount type, top-view type), and at 100 ° C. for 1 hour. Subsequently, it heated at 150 degreeC for 5 hours, and produced ten samples (henceforth the sample 1 for evaluation) in which the hardened | cured material was formed in the LED package. The obtained sample 1 for evaluation was placed in a thermo-hygrostat (product name “PL-3KP” manufactured by ESPEC) and held for 8 hours in an atmosphere of 85 ° C. and 85% RH, and then a solder reflow device (Senju Metal Industry Co., Ltd.) The product was heated at 260 ° C. for 20 seconds (high temperature and high humidity test) using a product name “STR-2010”). The presence or absence of cracks in the cured product after the high temperature and high humidity test was observed with an optical microscope, and the crack resistance after the high temperature and high humidity test was evaluated. Evaluation was performed according to the following criteria.
A: There were no cracks in any of the 10 samples.
B: There were cracks in 1 to 4 samples out of 10 samples.
C: There were cracks in 5 or more samples out of 10 samples.

3-3. Injecting crack resistance wherein after heat cycle test curable composition obtained in "2 tone made of the curable composition" LED package (surface mount, top-view type) in 1 hour at 100 ° C., Subsequently, it heated at 150 degreeC for 5 hours, and produced ten samples (henceforth the sample 2 for evaluation) in which the hardened | cured material was formed in the LED package. The obtained sample 2 for evaluation was heated from −40 ° C. to 100 ° C. (heating rate: 1 ° C./second) and 100 ° C. to −40 with a thermal shock test apparatus (trade name “TOM17” manufactured by ESPEC). 500 cycles of heating and cooling tests in which cooling at 0 ° C. (cooling rate: −1 ° C./second) was taken as one cycle were performed (heat cycle test). The presence or absence of cracks in the cured product after 500 cycles was observed with an optical microscope, and the crack resistance after the heat cycle test was evaluated. Evaluation was performed according to the following criteria.
A: There were no cracks in any of the 10 samples.
B: There were cracks in 1 to 4 samples out of 10 samples.
C: There were cracks in 5 or more samples out of 10 samples.

3-4. Gas barrier property against hydrogen sulfide The curable composition obtained in the above “2. Preparation of curable composition” is injected into an LED package (surface mount type, top view type), 100 ° C. for 1 hour, and then 150 ° C. Was heated for 5 hours to prepare a sample in which a cured product was formed in the LED package (hereinafter referred to as evaluation sample 3). The evaluation sample 3 was placed in a heating container filled with a gas containing 90% by volume of air and 10% by volume of hydrogen sulfide, and the evaluation sample 3 was heated at 80 ° C. for 24 hours. The appearance of the silver electrode of the LED package of the sample 3 for evaluation before and after heating was observed with an optical microscope, and the gas barrier property against hydrogen sulfide was evaluated. Evaluation was performed according to the following criteria.
A: There was no color change of the silver electrode before and after heating.
B: The silver electrode part became slightly yellow after heating.
C: After heating, the silver electrode portion was blackened.

3-5. Gas barrier property against water vapor After the curable composition obtained in “2. Preparation of curable composition” was coated on a release film, the release film was heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours. By peeling, a film-like cured product having a film thickness of 200 μm was formed. By measuring the water vapor transmission amount of this cured product with a MOCON water vapor transmission rate measuring device (manufactured by MOCON, trade name “PERMATRAN-W3 / 31”), and calculating the diffusion coefficient from (water vapor transmission amount × film thickness). The gas barrier property against water vapor was evaluated. Evaluation was performed according to the following criteria.
A: Water vapor diffusion coefficient is less than 16.
B: Water vapor diffusion coefficient is 16-20.
C: The water vapor diffusion coefficient is larger than 20.

  The curable composition of the present invention has high resistance to thermal shock, high temperature and high humidity environment, and can form a cured product that is less prone to cracking. Therefore, an optical semiconductor element and an encapsulant for an optical semiconductor member, It is useful as an adhesive, potting agent, protective coating agent, underfill agent and the like.

DESCRIPTION OF SYMBOLS 1 Optical semiconductor device 2 Semiconductor light emitting element 3 Reflector 4 Sealing material 5 Particle 6 Electrode 7 Wire

Claims (4)

A curable composition comprising a compound (A) represented by the following formula (1), a polysiloxane (B) represented by the following chemical formula (2), and a hydrosilylation catalyst (C).

(In the formula, n represents an integer of 1 or more. R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms. Ar represents an aryl group.)

(In the formula, R ^3, R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an aryl group or a group containing an epoxy group, a. Provided that at least 2 of all R ³ and R ⁶ one is an alkenyl group, R ⁵ may then another R ⁵ bonded to the silicon atom to which R ⁵ is attached is an aryl group, .R ⁴ not alkyl groups and aryl groups of 1 to 4 carbon atoms Each independently represents an alkyl or aryl group having 1 to 4 carbon atoms, and at least one of R ⁴ represents an aryl group, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a, c , E and f each independently represents an integer of 0 or more, b and d each independently represents an integer of 1 or more, provided that when a is 0, d is an integer of 2 or more.) The curable composition according to claim 1, wherein R ^{4 in the} chemical formula (2) is an aryl group.   A cured product obtained by curing the curable composition according to claim 1.   An optical semiconductor device having the cured product according to claim 3.

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