TWI513766B - Curable composition, cured product and optical semiconductor device - Google Patents

Description

Curable composition, cured product, and optical semiconductor device

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

Anthrone resin has been widely used as a sealing material for semiconductor elements including LED elements. The fluorenone resin is superior in heat resistance, transparency, and discoloration resistance as compared with the epoxy resin previously used as a sealing material, and on the other hand, mechanical properties such as bending strength are low, and thus the LED is energized or lit. Problems such as cracks are likely to occur due to thermal shock or high-temperature and high-humidity environments generated during the period.

As a technique for preventing the occurrence of such cracks, Patent Document 1 discloses an organic polyoxoxane composition containing at least two alkenyl groups bonded to a ruthenium atom in one molecule, and having a specific a polyorganosiloxane having a branched structure of a siloxane unit; a linear organohydrogenated polyfluorene having at least two hydrogen atoms bonded to a ruthenium atom in one molecule and having a viscosity of less than 1000 mPas at 25 ° C Oxygenane; addition reaction catalyst. Patent Document 2 discloses a polyorganosiloxane composition comprising: a linear polyorganosiloxane having a specific organic group and a branched polyorganosiloxane having a specific siloxane unit; a polyorganosiloxane having an alkenyl group; a molecule having a specific oxane unit A polyalkylhydroquinone oxide containing three or more hydrogen atoms bonded to a ruthenium atom; a platinum group metal compound.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-225715

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-335857

An object of the present invention is to provide a curable polyoxyalkylene composition which can form a cured product which is highly resistant to thermal shock or high-temperature and high-humidity conditions and which is less likely to cause cracks even in a severe environment.

The present invention is a hardenable composition characterized by comprising:

The compound (A) represented by the following formula (1), the polyoxyalkylene (B) represented by the following chemical formula (2), and the catalyst (C) for hydrogenation reaction (hydrosilylation reaction).

(wherein, 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.)

(R ³ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁵ ₂ SiO _2/2 ) _c (R ⁶ SiO _3/2 ) _d (SiO _4/2 ) _e (XO _1/2 ) _f (2)

(R ^3, R ⁵ and R ⁶ each independently represent an organic group wherein all of R ^3, and R is at least two ⁶ is an alkenyl group, R ⁵ on the silicon atoms of R ⁵ are bonded bonded to another When one R ⁵ is an aryl group, it is not an alkyl group having 1 to 4 carbon atoms and an aryl group. R ⁴ each independently represents an alkyl group or an 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 represent an integer of 0 or more. b and d each independently represent an integer of 1 or more. When it is 0, d is an integer of 2 or more.)

In the hardenable composition, it is preferred that R ⁴ of the chemical formula (2) is an aryl group.

Another invention is a cured product obtained by hardening the curable composition.

Yet another invention is an optical semiconductor device comprising the cured product.

The curable composition of the present invention can form a cured product which is highly resistant to thermal shock or high-temperature and high-humidity conditions and which is less likely to be cracked even in a severe environment.

Therefore, the optical semiconductor device obtained by coating the semiconductor light-emitting device with the cured product obtained from the curable composition is an optical semiconductor device excellent in reliability.

1‧‧‧Optical semiconductor device

2‧‧‧Semiconductor light-emitting elements

3‧‧‧ reflector

4‧‧‧ Sealing material

5‧‧‧ particles

6‧‧‧Electrode

7‧‧‧Wire

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

<Sclerosing composition>

The curable composition of the present invention contains the compound (A) represented by the following formula (1), the polyoxyalkylene (B) represented by the following chemical formula (2), and the catalyst (C) for hydrogenation reaction.

(wherein, 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.)

(R ³ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁵ ₂ SiO _2/2 ) _c (R ⁶ SiO _3/2 ) _d (SiO _4/2 ) _e (XO _1/2 ) _f (2)

(R ^3, R ⁵ and R ⁶ each independently represent an organic group wherein all of R ^3, and R is at least two ⁶ is an alkenyl group, R ⁵ on the silicon atoms of R ⁵ are bonded bonded to another When one R ⁵ is an aryl group, it is not an alkyl group having 1 to 4 carbon atoms and an aryl group. R ⁴ each independently represents an alkyl group or an 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 represent an integer of 0 or more. b and d each independently represent an integer of 1 or more. When it is 0, d is an integer of 2 or more.)

In the present invention, the term "polyoxyalkylene oxide" means a siloxane having a molecular skeleton in which two or more siloxane units (Si-O) are bonded.

Compound (A)

The compound (A) is a compound represented by the above formula (1). The compound (A) is a linear polyoxyalkylene having two hydrogen atoms bonded to a ruthenium atom per molecule. Hydrogen atoms bonded to the ruthenium atom are present in the oxoxane unit at both ends of the molecule. The compound (A) is a crosslinking agent for polyoxyalkylene (B), which is formed by hydrogenation reaction with polyfluorene oxide (B) to form a cured product.

R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms. That is, the compound (A) is a hydroquinone having one or more D units of a decane unit having a aryl group bonded to a ruthenium atom and having a carbon number of 1 to 4 Alkyl group. a compound (A) having such a D unit of a oxoxane unit and a hydroquinone having a siloxane unit having a D unit having 2 aryl groups, or a decane having a D unit having 2 alkyl groups The unit has a low crystallinity compared to the hydroquinone. Therefore, the cured product obtained by using the curable composition obtained by using the compound (A) and the polysiloxane (B) described above has a partially soft structure, and has high resistance to thermal shock or the like, and is difficult to produce. Cracked.

The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group or a t-butyl group. It is a methyl group.

Examples of the aryl group include an aromatic hydrocarbon group such as a phenyl group or a tolyl group, a thienyl group and a pyridyl group. Isoheteroaryl. Further, the hydrogen atom of the group such as a phenyl group as exemplified above may be substituted with a group such as a halogen atom or an alkyl group. When n in the formula (1) is an integer of 2 or more, the n Ar groups present in the formula (1) may be the same kind of aryl groups, or may be different kinds of aryl groups.

In the above formula (1), n represents an integer of 1 or more, and preferably an integer of 1 to 3.

The compound (A) can be, for example, alkoxydecane such as methylphenyldimethoxydecane or diphenyldimethoxydecane, and 1,1,3,3-tetramethyldifluoride by a known method. It is obtained by reacting hydroquinone such as oxyalkylene.

The content of the compound (A) in the curable composition of the present invention is preferably such that the amount of hydrogen atoms bonded to the ruthenium atom in the compound (A) is relative to the amount of the alkenyl group in the polysiloxane (B). The molar ratio is 0.1 to 5, more preferably 0.5 to 2, and even more preferably 0.7 to 1.4. When the content of the compound (A) is within the above range, it is easy to form a cured product which is highly resistant to thermal shock or the like and which is less likely to generate cracks, and the hardening of the composition proceeds sufficiently.

Polyoxane (B)

The polyoxyalkylene (B) is a polyoxyalkylene represented by the above formula (2). The polyoxyalkylene (B) is a main component of the present composition, and is hardened by hydrogenation reaction with the compound (A) to become a main component of the cured product.

In the above formula (2), R ³ , R ⁵ and R ⁶ each independently represent an organic group. The three R ³ contained in one oxoxane unit may be different organic groups, or two of them may be the same organic group, and the remaining one may be an organic group different therefrom, or may be three The same organic base. Further, when a is an integer of 2 or more, the plurality of siloxane oxide units including R ³ may be the same or different, or a part of the plurality may be the same or different from the other portions. The two R ⁵ contained in one oxoxane unit may be different organic groups or may be the same organic group. Further, when c is an integer of 2 or more, the plurality of siloxane units including R ⁵ may be the same or different, or a part of the plurality may be the same or different from the other portions. In the case where d is an integer of 2 or more, the plurality of oxane units including R ⁶ may be the same or different, or a part of the plurality may be the same or different from the other portions.

Examples of the organic group include an alkyl group, an alkenyl group, an aryl group and the like.

The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, and a t-butyl group. Preferred among these are methyl groups.

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

Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like, and among these, a phenyl group is preferred.

The organic group may also be a group containing an epoxy group. When the polyoxyalkylene (B) has a group containing an epoxy group as an organic group, it is difficult to prevent the hydrogenation reaction which occurs when the curable composition is cured, and it is possible to form a high adhesion to a substrate or a metal wiring or the like. Hardened material. Examples of the group having an epoxy group include glycidyloxy group such as glycidoxy group, 3-glycidoxypropyl group, and 3,4-epoxycyclopentyl group and 3,4-epoxy group. Cyclohexyl, An epoxycycloalkyl group such as 2-(3,4-epoxycyclopentyl)ethyl or 2-(3,4-epoxycyclohexyl)ethyl.

Among them, at least two of R ³ and R ⁶ contained in one molecule are alkenyl groups, and preferably two to four are alkenyl groups. That is, the polyoxyalkylene (B) has two or more alkenyl groups per molecule. R 2 or more may have a group other than an alkenyl group ^3, R ⁶ are alkylene group; R ³ may also be groups other than the alkenyl group are, of R ⁶ 2 or more alkenyl group; R ³ may One or more of them have an alkenyl group, and one or more of R ⁶ are an alkenyl group.

Also, R ⁵ in the silicon atoms of R ⁵ are bonded bonded to another R ⁵ is an aryl group, not carbon atoms of the alkyl group having 1 to 4 and an aryl group. I.e., R ⁵ comprises silicon of siloxane units containing silicon siloxane units R ⁴ is not the same.

In the above formula (2), two R ⁴ contained in one oxoxane unit each independently represent an alkyl group or an aryl group having 1 to 4 carbon atoms, and at least one of R ⁴ represents an aryl group. In the case where b is an integer of 2 or more, the plurality of siloxane oxide units including R ⁴ may be the same or different, or a part of the plurality may be the same or different from the other portions. That is, the polyoxyalkylene (B) has only one or more D units having an aryl group and an alkyl group having 1 to 4 carbon atoms bonded to a ruthenium atom as a arsonane unit containing R ⁴ ; One or more D units having two aryl groups bonded to a ruthenium atom as a arsonane unit containing R ⁴ ; or one or more aryl groups bonded to a ruthenium atom and an alkane having a carbon number of 1 to 4 A D unit having a D unit and having one or more aryl groups bonded to a ruthenium atom as a fluorene unit containing R ⁴ . By using such a polyoxyalkylene (B) having a D unit of a siloxane unit in combination with the above compound (A), it is possible to obtain a cured product which is highly resistant to thermal shock and is hard to be cracked. The hardening composition.

Further, if R ⁴ is an aryl group, that is, the polyoxyalkylene oxide (B) has only a D unit having two aryl groups bonded to a ruthenium atom as a siloxane group containing R ⁴ , it is difficult to form. The crack is preferable in terms of a cured product having a high gas barrier property to water vapor.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, and a t-butyl group. Some of the best ones are methyl groups.

Examples of the aryl group represented by R ⁴ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like, and among these, a phenyl group is particularly preferred.

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. Wherein, when a is 0, d is an integer of 2 or more. Since d is an integer of 1 or more, the polyoxyalkylene (B) necessarily has a T unit of a decane unit, and thus has a branched structure. Even if a polysiloxane having no branched structure is used in combination with the compound (A) to form a composition, the composition is hard to be hardened. Moreover, even in the case where the composition is hardened, 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 polyoxane (B) contained in the curable composition of the present invention is set to 100 in total of the components (A), (B) and (C) contained in the composition. When the mass is %, it is preferably 30% by mass to 95% by mass, more preferably 40% by mass. The mass % to 90% by mass, and more preferably 50% by mass to 80% by mass. When the content of the polyoxyalkylene (B) is within the above range, it is easy to form a cured product which is highly resistant to thermal shock or the like and which is less likely to cause cracks, and the hardening of the composition is sufficiently performed.

The polystyrene-equivalent weight average molecular weight of the polyoxyalkylene (B) measured by gel permeation chromatography is preferably in the range of from 100 to 50,000, more preferably in the range of from 500 to 5,000. The details of the measurement conditions of the gel permeation chromatography are as described in the examples. When the weight average molecular weight of the polyoxyalkylene (B) is within the above range, it is easy to handle when the sealing material is produced by using the composition, and the cured product obtained from the composition has a sufficient material as an optical semiconductor sealing material. Strength and characteristics.

The manufacturing method of the polyoxyalkylene (B) is exemplified by Japanese Patent Laid-Open No. Hei 6-9659, Japanese Patent Laid-Open Publication No. 2003-183582, Japanese Patent Laid-Open No. 2007-008996, and Japanese Patent Laid-Open No. 2007-106798. A known method described in, for example, Japanese Patent Publication No. 2007-169427, and Japanese Patent Laid-Open Publication No. 2010-059359, for example, a method of co-hydrolysis of chlorodecane or alkoxy decane which is a source of each unit, or A method of performing a balanced reaction of a co-hydrolyzate by an alkali metal catalyst or the like.

矽Hydrogenation catalyst (C)

The catalyst (C) for the hydrogenation reaction is a catalyst for the hydrogenation reaction of the compound (A) with the polyoxyalkylene (B).

The catalyst (C) for the hydrogenation reaction is not particularly limited as long as it is used as a catalyst for the hydrogenation reaction catalyst in the composition of the hydroquinone alkyl polysiloxane.

Specific examples of the catalyst (C) for hydrogenation reaction include platinum-based catalysts and rhodium-based catalysts. Medium, palladium system catalyst. From the viewpoint of promoting the hardening of the composition, preferred among these are platinum-based catalysts. Examples of the platinum-based catalyst include a platinum-alkenyl alkoxylate complex and the like. Examples of the alkenyl oxirane include 1,3-divinyl-1,1,3,3-tetramethyldioxane and 1,3,5,7-tetramethyl-1,3,5. 7-tetravinylcyclotetraoxane, and the like. Particularly, from the viewpoint of the stability of the self-aligned compound, 1,3-divinyl-1,1,3,3-tetramethyldioxane is preferred.

The content of the catalyst (C) for the hydrogenation reaction in the hardenable composition of the present invention is an amount in which the hydrogenation reaction of the compound (A) with the polyoxyalkylene (B) is actually carried out.

In addition to the above-mentioned components, the curable composition of the present invention may contain, for example, finely divided cerium oxide such as fired cerium oxide or quartz powder, or inorganic filler such as titanium oxide or zinc oxide. a retarder such as cyclotetramethyltetravinyltetraoxane, a diluent such as diphenyl bis(dimethylvinyl decyloxy) decane or phenyl tris(dimethylvinyl decyloxy) decane , phosphors, pigments, flame retardants, heat-resistant agents, antioxidants, etc.

The curable composition of the present invention can be prepared by uniformly mixing the components by a known method such as a mixer.

The viscosity of the curable composition of the present invention at 25 ° C is preferably 1 mPa. s~1000000 mPa. s, more preferably 10 mPa. s~10000 mPa. s. When the viscosity is within this range, the workability of the composition is improved.

The curable composition of the present invention can be prepared into one liquid, or can be separately prepared into two liquids, and the two liquids can be used in combination at the time of use. A small amount of a hardening inhibitor such as acetylene alcohol may also be added as needed.

<hardened matter>

The cured product is obtained by curing the curable composition of the present invention. When the semiconductor element is sealed and hardened by the curable composition of the present invention, a cured product as a sealing material is obtained.

The method of curing the curable composition of the present invention is, for example, a method in which the curable composition is applied onto a substrate, and then heated at 100 ° C to 180 ° C for 1 hour 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 or the like, and is unlikely to be cracked even in a severe environment.

<Optical semiconductor device>

The optical semiconductor device of the present invention contains 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 material covering the semiconductor light emitting element. The optical semiconductor device of the present invention can be obtained by coating the curable composition on a semiconductor light-emitting device to harden the composition. The method of hardening the curable composition is as described above.

Examples of the optical semiconductor device include a light emitting diode (LED), a laser diode (LD), and the like.

Fig. 1 is a schematic view showing a specific example of an optical semiconductor device of the present invention. The optical semiconductor device 1 includes an electrode 6 which is a silver electrode or the like, a semiconductor light-emitting element 2 which is provided on the electrode 6, and is electrically connected to the electrode 6 via a wire 7; and the reflector 3 is provided to house the semiconductor light-emitting device 2 The sealing member 4 is filled in the reflector 3 to seal the semiconductor light emitting element 2. The sealing material 4 contains a cured product obtained by curing the curable composition of the present invention. Particles 5 such as cerium oxide or a phosphor are dispersed in the sealing material 4.

As described above, the cured product obtained by curing the curable composition of the present invention is hard to be cracked even in a severe environment, and therefore the optical semiconductor device having the cured product as a sealing material is subjected to thermal shock conditions. It can also be used under low temperature or high humidity conditions.

[Examples] 1. Preparation of hardenable composition

1-1. Structural analysis

The structure of the synthesized compound can be calculated by ²⁹ Si NMR and ¹³ C NMR.

1-2. Weight average molecular weight

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions, and was determined as a polystyrene-converted value.

Device: HLC-8120C (manufactured by Tosoh Corporation)

Column: TSK-gel MultiporeHXL-M (made by Tosoh Corporation)

Dissolution: THF, flow rate 0.5 mL/min, loading 5.0%, 100 μL

1-3. Synthesis of each component

The oxoxane units listed below are represented by the symbols shown below.

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)

Put 455 g of methylphenyldimethoxydecane, 0.1 g of trifluoromethanesulfonic acid, 336 g of 1,1,3,3-tetramethyldioxane in the reaction kettle, followed by adding 180 g of acetic acid. The reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain the compound (A1) shown below.

[Synthesis Example 2] Synthesis of Compound (A2)

300 g of methylphenyldimethoxydecane, 0.1 g of trifluoromethanesulfonic acid and 450 g of 1,1,3,3-tetramethyldioxane were placed in the reaction vessel, followed by the addition of 100 g of acetic acid. The reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain the compound (A2) shown below.

[Chemical 4]

[Synthesis Example 3] Synthesis of Compound (A3)

656 g of methylphenyldimethoxydecane, 0.1 g of trifluoromethanesulfonic acid, and 188 g of 1,1,3,3-tetramethyldioxane were placed in the reaction vessel, followed by the addition of 280 g of acetic acid. The reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain the compound (A3) shown below.

[Synthesis Example 4] Synthesis of Compound (D1)

Put 403 g of diphenyldimethoxydecane, 0.1 g of trifluoromethanesulfonic acid, 450 g of 1,1,3,3-tetramethyldioxane in the reaction vessel, and then add 130 g of acetic acid. The reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain the compound (D1) shown below.

[Chemical 6]

[Synthesis Example 5] Synthesis of Compound (D2)

Put 403 g of diphenyldimethoxydecane, 40 g of dimethoxydimethyloxane, 0.1 g of trifluoromethanesulfonate, 1,1,3,3-tetramethyldi in the reaction kettle. 450 g of decane, followed by addition of 130 g of acetic acid, was carried out at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain the compound (D2) shown below.

[Synthesis Example 6] Synthesis of polyoxyalkylene (B1)

1,3-divinyl-1,1,3,3-tetramethyldioxane 186 g, phenyltrimethoxydecane 594 g, methylphenyldimethoxydecane were placed in the reaction vessel. 182 g, 180 g of water, 0.8 g of trifluoromethanesulfonic acid, and 650 g of toluene were heated under reflux for 1 hour. Next, 1 g of 3-glycidoxypropylmethyldimethoxydecane and 0.6 g of potassium hydroxide were added. Heated back under 5 hours. After being neutralized by an acid, it is washed with water to obtain a polyoxane (B1) containing T(Ph) 60 mol, D(MePh) 20 mol, and D(MeEp) 0.1 mol relative to M(Vi) 20 mol. ). The polyoxyalkylene (B1) has a weight average molecular weight of 1,400.

[Synthesis Example 7] Synthesis of polyoxyalkylene (B2)

1,3-divinyl-1,1,3,3-tetramethyldioxane 186 g, phenyltrimethoxydecane 595 g, diphenyldimethoxydecane 244 were placed in the reaction vessel. g, 200 g of water, 0.8 g of trifluoromethanesulfonic acid and 700 g of toluene were heated under reflux for 1 hour. Next, 0.6 g of potassium hydroxide was added thereto for reflux for 5 hours. After neutralization by acetic acid, water washing was carried out to obtain a polyoxane (B2) containing T(Ph) 60 mol and D(Ph) 20 mol with respect to 20 mol of M(Vi). The polyoxyalkylene (B2) has a weight average molecular weight of 1,500.

[Synthesis Example 8] Synthesis of polyoxyalkylene (D3)

In the reaction vessel, 183 g of diphenyldimethoxydecane, 0.6 g of trifluoromethanesulfonic acid, and 1,3-divinyl-1,1,3,3-tetramethyldioxane 140 g were placed. After the addition of 40 g of acetic acid, the reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain the compound (D4) shown below.

[Synthesis Example 9] Synthesis of polyoxyalkylene (B3)

147 g of phenyltrimethoxydecane, 183 g of diphenyldimethoxydecane, 0.6 g of trifluoromethanesulfonic acid, and 1,3-divinyl-1,1,3,3-tetra were added to the reaction vessel. Methyldioxane 653 g, followed by the addition of 40 g of acetic acid, was reacted at 50 ° C for 3 hours. After completion of the reaction, liquid separation extraction was carried out using toluene and water to obtain a polyoxane (B3) containing 15 mol of T(Ph) and 15 mol of D(Ph) relative to M(Vi) 70 mol. The polyoxyalkylene (B3) has a weight average molecular weight of 500.

2. Modulation of hardening composition [Example 1 to Example 5 and Comparative Example 1 to Comparative Example 3]

The components shown in the following Table 1 were mixed in the amounts shown in Table 1, and the curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were obtained. The "parts" in Table 1 represent parts by mass. Further, the molar ratio of the amount of hydrogen atoms bonded to the ruthenium atom in the compound (A) to the amount of the alkenyl group in the polysiloxane (B) was 1.05. Further, the details of the respective components in Table 1 are as follows.

Catalyst for hydrogenation reaction (C1): a complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldioxane (the amount of platinum metal is 4% by mass)

Compound (D4): cyclotetramethyltetravinyltetraoxane

Compound (D5): diphenyl bis(dimethylvinyl decyloxy) decane

Compound (D6): Phenyltris(dimethylvinylnonyloxy)decane

3. Evaluation of hardening composition

The curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated by the following methods (3-1) to (3-6). The evaluation results are shown in Table 2.

3-1. Heat resistance

After applying the curable composition obtained in "2. Preparation of curable composition" to quartz glass, heating was performed at 100 ° C for 1 hour, followed by 150 ° C. Heating for 5 hours was carried out to form a cured product having a film thickness of 1 mm on the quartz glass. The heat resistance was evaluated by visually observing the appearance of the cured product at 150 ° C for about 500 hours. The evaluation was performed on the basis of the following criteria.

A: There is no color change before and after storage.

B: Slightly yellow after storage.

C: Apparently yellowed after storage.

3-2. Crack resistance after high temperature and high humidity test

The curable composition obtained in the "2. Preparation of the curable composition" was injected into an LED package (surface adhesion type, top view type), and heated at 100 ° C for 1 hour, followed by heating. The film was heated at 150 ° C for 5 hours to prepare 10 samples (hereinafter referred to as sample for evaluation 1) in which a cured product was formed in the LED package. The obtained sample for evaluation 1 was placed in a constant temperature and humidity chamber (manufactured by ESPEC, trade name "PL-3KP"), and kept at 85 ° C and 85% RH for 8 hours. Using a reflow soldering apparatus (manufactured by Senju Metal Industry Co., Ltd., trade name "STR-2010"), heating was performed at 260 ° C for 20 seconds (high temperature and high humidity test). The crack resistance of the cured product after the high-temperature and high-humidity test was evaluated by observing the presence or absence of the crack of the cured product after the high-temperature and high-humidity test by an optical microscope. The evaluation was performed on the basis of the following criteria.

A: No cracks were found in any of the 10 samples.

B: There is a crack in one to four of the 10 samples.

C: Cracks were present in more than 5 of the 10 samples.

3-3. Crack resistance after thermal cycle test

The hardenable composition obtained in the "2. Modification of the curable composition" is described. Into the LED package (surface adhesion type, top view type), heating was performed at 100 ° C for 1 hour, followed by heating at 150 ° C for 5 hours, and 10 samples of the cured product formed in the LED package were produced (below It is called sample for evaluation 2). For the obtained evaluation sample 2, heating was performed at -40 ° C to 100 ° C for 500 cycles by a thermal shock test apparatus (manufactured by ESPEC, trade name "TOM 17") (heating rate was 1 ° C) /sec), cooling at 100 ° C to -40 ° C (cooling rate -1 ° C / sec) is a one-cycle heating and cooling test (thermal cycle test). The crack resistance of the cured product after 500 cycles was observed by an optical microscope, and the crack resistance after the heat cycle test was evaluated. The evaluation was performed on the basis of the following criteria.

A: No cracks were found in any of the 10 samples.

B: There is a crack in one to four of the 10 samples.

C: Cracks were present in more than 5 of the 10 samples.

3-4. Gas barrier to hydrogen sulfide

The curable composition obtained in the "2. Preparation of the curable composition" was injected into an LED package (surface adhesion type, plan view type), heated at 100 ° C for 1 hour, and then at 150 ° C. After heating for 5 hours, a sample in which a cured product was formed in the LED package (hereinafter referred to as sample for evaluation 3) was produced. The sample for evaluation 3 was placed in a heating vessel filled with a gas containing 90 vol% (by volume) of air and 10 vol% of hydrogen sulfide, and the sample for evaluation 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 by an optical microscope, and the gas barrier property against hydrogen sulfide was evaluated. The evaluation was performed on the basis of the following criteria.

A: There is no color change of the silver electrode before and after heating.

B: After heating, the silver electrode portion was slightly yellowed.

C: After heating, the silver electrode portion is blackened.

3-5. Gas barrier to water vapor

The curable composition obtained in the "2. Preparation of a curable composition" is applied onto a release film, and then heated at 100 ° C for 1 hour, followed by heating at 150 ° C for 5 hours. The release film was peeled off, whereby a film-like cured product having a film thickness of 200 μm was formed. The water vapor transmission amount of the cured product is measured by a MOCON water vapor transmission rate measuring device (manufactured by MOCON Corporation, trade name "PERMATRAN-W3/31"), and the diffusion coefficient is calculated from (water vapor transmission amount × film thickness). Evaluation of gas barrier properties to water vapor. The evaluation was performed on the basis of the following criteria.

A: The water vapor diffusion coefficient is less than 16.

B: The water vapor diffusion coefficient is 16-20.

C: The water vapor diffusion coefficient is greater than 20.

The curable composition of the present invention can form a cured product which is highly resistant to thermal shock or high-temperature and high-humidity environments and which is less likely to cause cracks, and thus can be used as an optical semiconductor. A sealing agent, an adhesive, a potting agent, a protective coating agent, an underfill, and the like of the element and the optical semiconductor member.

1‧‧‧Optical semiconductor device

2‧‧‧Semiconductor light-emitting elements

3‧‧‧ reflector

4‧‧‧ Sealing material

5‧‧‧ particles

6‧‧‧Electrode

7‧‧‧Wire

Claims (4)

A curable composition comprising a compound (A) represented by the following formula (1), a polyoxyalkylene (B) represented by the following chemical formula (2), and a catalyst for hydrogenation reaction of hydrazine ( C), (wherein, n represents an integer of 1 or more; R ¹ and R ² represent an alkyl group having a carbon number of 1 to 4; and Ar represents an aryl group) [Chemical 2] (R ³ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁵ ₂ SiO _2/2 ) _c (R ⁶ SiO _3/2 ) _d (SiO _4/2 ) _e (XO _1/2 ) _f (2) (R ³ , R ⁵ and R ⁶ independently represents an organic group, which is an alkyl group, an alkenyl group, an aryl group or an epoxy group; wherein, at least two of all R ³ and R ⁶ are alkenyl groups, and R ^{5 is} in this R ⁵ When the other R ⁵ bonded to the bonded ruthenium atom is an aryl group, it is not an alkyl group having a carbon number of 1 to 4 and an aryl group; and R ⁴ each independently represents an alkyl group or a aryl group having a carbon number of 1 to 4; a group, 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 represent an integer of 0 or more; b and d are independently An integer of 1 or more is represented; wherein, when a is 0, d is an integer of 2 or more). The curable composition according to claim 1, wherein R ⁴ of the chemical formula (2) is an aryl group. A cured product obtained by curing a curable composition according to the first or second aspect of the patent application. An optical semiconductor device comprising the cured product according to claim 3 of the patent application.