TW201323524A - Curable composition, cured object and optical semiconductor device - Google Patents

Abstract

A curable composition includes: a polysiloxane (A) of specific structure having at least two alkenyl groups, a polysiloxane (B) having at least one or more siloxanes of two aryl groups bonded to the same silicon atom which for forming polysiloxane chain and a catalyst for a hydrosilation reaction (C). The curable composition of the invention forms a cured object excellent in moisture resistance. Even when an optical semiconductor, which includes the cured object formed by the curable composition of the invention as a sealing material and so on, is used for long period, the possibility of decrease in emitting property of an emitting device due to permeation of water vapor is small.

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.

As a sealing agent for a semiconductor light-emitting device such as an LED, there is a composition of a hydrazine hydrogenation reaction-curable fluorenone-based resin, and an fluorenone-based resin having high durability against heat or light is used. The hydrogenation-reaction-curable fluorenone-based resin composition preferably has a good curability and can form a cured product having a large refractive index and a high light transmittance, high adhesion to a substrate, high hardness, and low surface viscosity.

As such an anthrone-based resin composition, Patent Document 1 discloses a curable organopolyoxane composition containing a specific linear diorganopolyoxyalkylene group and a specific branched organic polycondensation. A siloxane which has at least two aryl groups bonded to a ruthenium atom in one molecule and an organopolyoxy siloxane having at least two hydrogen atoms bonded to a ruthenium atom, and a catalyst for hydrogenation reaction.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-050494

However, the conventional anthrone-based resin has a disadvantage of poor moisture resistance, and when the light-emitting element is sealed with an anthrone-based resin composition, there is a problem that water vapor is transmitted through the sealing material due to long-term use, and the light-emitting characteristics of the light-emitting element are generated. reduce.

An object of the present invention is to provide a curable composition containing an anthrone-based resin which can form a cured product excellent in moisture resistance, and an optical semiconductor device including the cured product.

The present invention for achieving the object is as follows.

[1] A curable composition comprising a polyoxyalkylene (A) having at least two alkenyl groups represented by the following formula (1) and a polyoxyalkylene represented by the following formula (2) ( B), and a catalyst for hydrogenation reaction (C), [Chemical Formula 1] (R ¹ ₃ SiO _1/2 ) _a (R ^Ar1 ₂ SiO _2/2 ) _b (R ² ₂ SiO _2/2 ) _c (R ³ SiO _3/2 ) _d (SiO _4/2 ) _e (XO _1/2 ) _f (1)

(Wherein, R ^1, R ² and R ³ each independently represent an alkyl group, an alkenyl group, an aryl group, or adhesiveness with the substrate; wherein, on the same silicon atom bonded to two of R ² wherein R ² is a In the case of an aryl group, the other R ² is not an aryl group; moreover, at least two of all of R ¹ , R ² and R ³ are alkenyl groups; R ^Ar1 represents an aryl group; X represents a hydrogen atom or has a carbon number of 1 to 3 Alkyl; 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 R ⁴ each independently represents a monovalent hydrocarbon group; R ^Ar2 each independently represents an aryl group; and n represents an integer of 1 or more).

[2] The curable composition according to the above [1], wherein the polyoxyalkylene (B) is a compound of n≧2 in the above formula (2).

[3] The curable composition according to the above [1] or [2], wherein the content of the polyoxyalkylene (B) is 10 parts by mass based on 100 parts by mass of the polyoxyalkylene (A). Parts by mass to 100 parts by mass.

[4] A cured product obtained by curing the curable composition according to any one of the above [1] to [3].

[5] An optical semiconductor device comprising: a semiconductor light-emitting device; and the cured product according to [4] above which the semiconductor light-emitting device is coated.

The curable composition of the present invention can form a cured product excellent in moisture resistance. Even if the optical semiconductor device including the cured product formed of the curable composition of the present invention as a sealing material is used for a long period of time, the light-emitting characteristics of the light-emitting element may be lowered due to the transmission of water vapor.

<Sclerosing composition>

The curable composition of the present invention contains a polyoxyalkylene (A) having at least two alkenyl groups represented by the following formula (1), and a polyoxyalkylene (B) represented by the following formula (2). Catalyst for hydrogenation reaction (C), [Chemical Formula 1] (R ¹ ₃ SiO _1/2 ) _a (R ^Ar1 ₂ SiO _2/2 ) _b (R ² ₂ SiO _2/2 ) _c (R ³ SiO _3/2 ) _d (SiO _4/2 ) _e (XO _1/2 ) _f (1)

(Wherein, R ^1, R ² and R ³ each independently represent an alkyl group, an alkenyl group, an aryl group, or adhesiveness with the substrate. Wherein, on the same silicon atom bonded to two of R ² wherein R ² is a In the case of an aryl group, the other R ² is not an aryl group. Further, at least two of all of R ¹ , R ² and R ³ are alkenyl groups. R ^Ar1 represents an aryl group. X represents a hydrogen atom or has a carbon number of 1 to 3 The alkyl groups 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)

(In the formula, four R ⁴ each independently represent a monovalent hydrocarbon group. R ^Ar2 each independently represents an aryl group. n represents an integer of 1 or more).

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

Polyoxane (A)

The polyoxyalkylene (A) is a polyoxyalkylene having at least two alkenyl groups represented by the above formula (1). The polyoxyalkylene (A) is a main component of the present composition and is hardened by hydrogenation reaction with a polyhydrazine (B) to form a main body of the cured product.

In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group, an alkenyl group, an aryl group or an adhesive group. That is, with respect to one oxoxane unit (structural unit) having the symbol a, the three R ¹ present may independently be an alkyl group, an alkenyl group, an aryl group, or a close contact. Sexual basis. For example, in the three R ¹ in R ¹ is two or more are alkyl groups, the alkyl group may be the same alkyl group, an alkyl group may also be different. In the case where the symbol a is an integer of 2 or more, each of the decane units attached with the symbol a may be the same or different. R ² and R ^{3 are} also the same as R ¹ .

Wherein R ¹ present in the oxoxane unit attached with the symbol a, R ² present in the oxoxane unit attached with the symbol c, and R ³ present in the fluorinated alkane unit having the symbol d At least two of them are alkenyl groups, and at least two alkenyl groups are present in one molecule of the polyoxyalkylene (A) represented by the above formula (1). For example, one of the three R ¹ present in one oxoxane unit to which the symbol a is attached may be an alkenyl group, and two or more of the decane units may be present. Two or more of the three R ¹ present in one oxoxane unit to which the symbol a is attached may be an alkenyl group, and one or more of the decane units may be present. One of the three R ^{1 's} present in one oxoxane unit to which the symbol a is attached may be an alkenyl group, and one of the oxoxane units may be present in one oxoxane unit having the symbol c One of the two R ² present is an alkenyl group, and one or more of the decane units are present.

Further, in the case of the oxime unit having the symbol c, in the case where one of R ² of the two R ² bonded to the same fluorene atom is an aryl group, the other R ² is not an aryl group.

The alkyl group may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Borneol base, norbornyl base, adamantyl and the like. Among these groups, a methyl group is preferred.

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. Among these groups, a vinyl group, an allyl group, and a hexenyl group are preferable.

The aryl group may, for example, be a phenyl group, a tolyl group, a xylyl group or a naphthyl group. Phenyl groups are preferred among these groups.

The adhesion-bonding group is a group having adhesion to a metal or an organic resin which is a material such as a substrate of a semiconductor device or the like.

Examples of the adhesion group include a group having an epoxy group, a sulfinylene group, an isocyanate group, or a triallyl isocyanate group. Among these bases, a group having an epoxy group is preferred because it is difficult to prevent the hydrogenation reaction which occurs when the curable composition is cured.

Examples of the group having an epoxy group include glycidoxy, glycidoxyalkyl groups such as 3-glycidoxypropyl group, and 3,4-epoxycyclopentyl group, 3,4-. An epoxycycloalkyl group such as epoxycyclohexyl group, 2-(3,4-epoxycyclopentyl)ethyl group or 2-(3,4-epoxycyclohexyl)ethyl group. Specific examples of the group having an epoxy group include the groups represented by the following structural formulae (3) to (6). When the group having an epoxy group is such a group, it becomes possible to form a cured product at a level of mm.

[In the structural formula (3), R ⁵ represents a methylene group or a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms]

[In the structural formula (4), R ⁶ represents a methylene group or a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms]

[In the structural formula (5), R ⁷ represents a methylene group or a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms]

[In the structural formula (6), R ⁸ represents a methylene group or a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms]

Specific examples of the group represented by the structural formula (1) include 2-(3,4-epoxycyclohexyl)ethyl and the like.

Specific examples of the group represented by the structural formula (2) include a glycidyl group and the like.

Specific examples of the group represented by the structural formula (3) include 3-glycidoxypropyl group and the like.

Specific examples of the group represented by the structural formula (4) include 2-(4-methyl-3,4-epoxycyclohexyl)ethyl and the like.

In the formula (1), R ^Ar1 represents an aryl group. The aryl group represented by R ^{Ar1 is the same} as the aryl group represented by the above R ¹ , R ² and R ³ .

In the formula (1), X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the formula (1), 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.

The polyoxyalkylene (A) has a siloxane unit attached with the symbol b, that is, a siloxane unit having two aryl groups bonded to the same fluorene atom constituting the polyoxyalkylene chain, and thus is composed of the present hardenability. The moisture resistance of the cured product obtained by the material is improved.

When the total of a, b, c, d, e, and f is 100%, the ratio of a is preferably 0% to 60%, and more preferably 10% to 40%. The proportion of b is preferably 5% to 50%, more preferably 5% to 40%. The proportion of c is preferably from 0% to 40%, more preferably from 0% to 30%. The ratio of d is preferably from 30% to 90%, more preferably from 40% to 80%. The ratio of e is preferably from 0% to 40%, more preferably from 0% to 20%. The ratio of f is preferably from 0% to 50%, more preferably from 0.1% to 20%.

Polyphenylene oxide (A) as determined by gel permeation chromatography The weight average molecular weight in terms of ethylene is preferably in the range of 100 to 50,000, and more preferably in the range of 500 to 10,000. When the weight average molecular weight of the polyoxyalkylene (A) is within the above range, it is easy to handle when the sealing material is produced using the composition, and the cured product obtained from the composition has sufficient strength as an optical semiconductor sealing material.

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

Polysiloxane (B)

The polysiloxane (B) is a polysiloxane represented by the above formula (2). The polyoxyalkylene (B) is a crosslinking agent with respect to the polyoxyalkylene (A), and is formed by a hydrogenation reaction with a polyhydrazine (A).

In the formula (2), R ^Ar2 represents an aryl group. The aryl group may, for example, be a phenyl group, a tolyl group, a xylyl group or a naphthyl group. Phenyl groups are preferred among these groups.

In the formula (2), R ⁴ each independently represents a monovalent hydrocarbon group. The monovalent hydrocarbon group may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; An aralkyl group such as ethyl; a substituted alkyl group such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or nonafluorobutylethyl.

In the formula (2), n represents an integer of 1 or more. n is preferably an integer of 2 or more, more preferably an integer of 2 to 5, and still more preferably 2. When n is in the above range, a cured product excellent in moisture resistance can be obtained.

Since the polyoxyalkylene (B) has one or more siloxane units in which two aryl groups are bonded to the same fluorene atom constituting the polyoxyalkylene chain, the moisture resistance of the cured product obtained from the sclerosing composition is high. improve. That is, the present sclerosing composition is obtained by a polysiloxane (A) having the aryl group bonded to the same fluorene atom constituting the polyoxyalkylene chain. An oxane unit), a polyoxyalkylene (B) having at least one siloxane group bonded to two aryl groups on the same fluorene atom constituting the polyoxyalkylene chain Used in combination to improve the moisture resistance of the cured product.

The polyoxyalkylene (B) can be, for example, dihydrodialkyloxydecane such as diphenyldimethoxydecane and dihydrogen such as 1,1,3,3-tetramethyldioxane by a known method. Obtained by the reaction of a decane.

The content of the polyoxyalkylene (B) in the curable composition of the present invention is preferably 10 parts by mass to 100 parts by mass, more preferably 10 parts by mass, per 100 parts by mass of the polysiloxane (A). ~80 parts by mass. When the content of the polyoxyalkylene (B) is within the above range, the hardening of the composition proceeds sufficiently, and the obtained cured product obtains sufficient moisture resistance.

Rhodium catalyst for hydrogenation (C)

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

The catalyst for hydrogenation reaction (C) is used as a catalyst for hydrogenation reaction in the composition of the previous hydrogenation-reacting type anthrone-based resin. The catalyst to be used can be used without particular limitation.

Specific examples of the catalyst (C) for the hydrogenation reaction include a platinum catalyst, a rhodium catalyst, and a palladium catalyst. From the viewpoint of the hardening promotion of the present composition, a platinum-based catalyst is preferred among the catalysts. Examples of the platinum-based catalyst include a platinum-alkenyloxyalkylene complex and the like. Examples of the alkenyl alkane include 1,3-divinyl-1,1,3,3-tetramethyldioxane, 1,3,5,7-tetramethyl-1,3,5,7. - tetravinylcyclotetraoxane, and the like. In particular, from the viewpoint of stability of the complex, 1,3-divinyl-1,1,3,3-tetramethyldioxane is preferred.

The catalyst for the hydrogenation reaction of the hydrazine in the curable composition of the present invention (C) is an amount actually used in the hydrogenation reaction of polyfluorene oxide (A) with polysiloxane (B), for example, in the curable composition. 0.01 ppm~10000 ppm.

The curable composition of the present invention may contain, for example, gas phase cerium oxide, quartz powder, titanium oxide, aluminum oxide, zinc oxide, phosphor, etc., as long as it can achieve the object of the invention. a reaction retarder such as ethynylcyclohexanol or cyclo-tetramethyltetravinyltetraoxane, diphenylbis(dimethylvinyldecyloxy)decane, phenyltris(dimethylethene) Diluents such as decyloxy)decane, diphenylbis(dimethylhydroxydecyloxy)decane, pigments, flame retardants, heat-resistant agents, antioxidants, and the like.

The curable composition of the present invention can be prepared by uniformly mixing the above 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, and can also be divided into two liquids. The preparation was carried out by mixing two liquids at the time of use. A small amount of a hardening inhibitor such as acetylene alcohol such as ethynylcyclohexanol may be added as needed.

<hardened matter>

The cured product is obtained by curing the curable composition of the present invention.

The method of hardening the curable composition of the present invention is, for example, a method in which a curable composition is applied onto a substrate and then heated at 100 ° C to 180 ° C for 1 hour to 13 hours.

<Optical semiconductor device>

An optical semiconductor device according to 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 the curable composition on the semiconductor light-emitting device and curing the composition. The method of hardening the hardenable 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; the semiconductor light-emitting device 2 is disposed on the electrode 6, and is electrically connected to the electrode 6 via a wire 7; the reflector 3 is disposed to house the semiconductor light-emitting device 2; and the sealing member 4 The semiconductor light-emitting element 2 is sealed by being filled in the reflector 3. The sealing material 4 is obtained by hardening 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 curable composition of the present invention is cured. Since the sealing material (cured material) has high moisture resistance, even if the optical semiconductor device of the present invention is used for a long period of time, water vapor permeates through the sealing material to lower the light-emitting characteristics of the light-emitting element.

[Example] (1) Synthesis of polyoxyalkylene oxide

The structure of the polyoxyalkylene was determined by ²⁹ Si NMR and ¹³ C NMR.

The weight average molecular weight (Mw) of the polyoxyalkylene was measured by gel permeation chromatography (GPC) under the following conditions, and was determined to be a value in terms of polystyrene.

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

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

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

[Synthesis Example 1] Synthesis of Polysiloxane (A-1)

1,3-divinyl-1,1,3,3-tetramethyldioxane 37.3 g, phenyltrimethoxy group was placed in a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer. 234 g of decane, 97.7 g of diphenyldimethoxydecane, 55 g of water, 0.3 g of trifluoromethanesulfonic acid and 146 g of toluene were mixed, and heated under reflux at 66 ° C for 1 hour. After cooling to room temperature, the lower layer was separated and removed, and the upper layer of the toluene solution was washed with water. 30 g of water, 0.3 g of potassium hydroxide and 4.4 g of 3-glycidoxypropylmethyldimethoxydecane were added to the water-washed toluene solution layer, and heating was carried out at 70 ° C for 1 hour. Then, methanol was distilled off, and excess water was removed by azeotropic dehydration. Then, heating and refluxing was carried out at 111 ° C for 4 hours. The toluene solution after the reaction was cooled to room temperature, and then neutralized with 0.3 g of acetic acid to wash with water. After removing water, the toluene was distilled off under reduced pressure and concentrated to obtain an average unit formula (ViMe ₂ SiO _1/2 ) ₂₀ (PhSiO _3/2 ) ₅₉ (Ph ₂ SiO _2/2 ) ₂₀ (EpMeSiO _{2/2 1} (Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Ep represents a glycidoxypropyl group) represented by polyoxyalkylene oxide (A-1). The polyoxyalkylene (A-1) had a weight average molecular weight of 1,600.

[Synthesis Example 2] Synthesis of polyoxyalkylene (A-2)

1,3-divinyl-1,1,3,3-tetramethyldioxane 37.3 g, phenyltrimethoxy group was placed in a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer. 234 g of decane, 24 g of dimethyldimethoxydecane, 48.9 g of diphenyldimethoxydecane, 56 g of water, 0.3 g of trifluoromethanesulfonic acid and 133 g of toluene were mixed at 66 ° C. Heated back for 1 hour. After cooling to room temperature, the lower layer was separated and removed, and the upper layer of the toluene solution was washed with water. After removing water, the toluene was distilled off under reduced pressure and concentrated to obtain an average unit formula of (ViMe ₂ SiO _1/2 ) ₂₀ (PhSiO _3/2 ) ₆₀ (Me ₂ SiO _2/2 ) ₁₀ (Ph ₂ SiO). _2/2 ) ₁₀ (Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group) represented by polyoxyalkylene oxide (A-2). The polyoxyalkylene (A-2) had a weight average molecular weight of 1,600.

[Synthesis Example 3] Synthesis of Polyoxane (RA-1)

1,3-divinyl-1,1,3,3-tetramethyldioxane 37.3 g, phenyltrimethoxy group was placed in a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer. 234 g of decane, 48.1 g of dimethyldimethoxydecane, 56 g of water, 0.3 g of trifluoromethanesulfonic acid and 120 g of toluene were mixed and heated under reflux at 66 ° C for 1 hour. After cooling to room temperature, the lower layer was separated and removed, and the upper layer of the toluene solution was washed with water. 30 g of water, 0.3 g of potassium hydroxide and 4.4 g of 3-glycidoxypropylmethyldimethoxydecane were added to the water-washed toluene solution layer, and the mixture was heated under reflux at 70 ° C for 1 hour. Then, methanol was distilled off, and excess water was removed by azeotropic dehydration. Then, heating and refluxing was carried out at 111 ° C for 4 hours. The toluene solution after the reaction was cooled to room temperature, and then neutralized with 0.3 g of acetic acid to wash with water. After removing the water, the toluene was distilled off under reduced pressure and concentrated to obtain an average unit formula (ViMe ₂ SiO _1/2 ) ₂₀ (PhSiO _3/2 ) ₅₉ (Me ₂ SiO _2/2 ) ₂₀ (EpMeSiO _{2/2 1} (Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Ep represents a glycidoxypropyl group) represented by a polyoxyalkylene oxide (RA-1). The polyoxyalkylene (RA-1) has a weight average molecular weight of 1800.

[Synthesis Example 4] Synthesis of polyoxyalkylene (B-1)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 220 g of diphenyldimethoxydecane and 0.6 g of trifluoromethanesulfonic acid were added and mixed, and 1,1,3,3- was added. 60.5 g of tetramethyldioxane was added dropwise to 108 g of acetic acid over 30 minutes while stirring at room temperature. After completion of the dropwise addition, the mixture was heated to 50 ° C while stirring the mixture, and the reaction was carried out for 3 hours. Next, the temperature was raised to 80 ° C and allowed to react for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and then toluene and water were added thereto, and the mixture was thoroughly mixed, and then allowed to stand, and the aqueous layer was separated and removed. The toluene solution layer of the upper layer was washed with water three times, and then concentrated under reduced pressure to obtain a polyoxane (B-1) represented by the following formula (7).

[Chemistry 7]

[Synthesis Example 5] Synthesis of polysiloxane (B-2)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 220 g of diphenyldimethoxydecane and 0.6 g of trifluoromethanesulfonic acid were added and mixed, and 1,1,3,3- was added. 147 g of tetramethyldioxane was added dropwise to 108 g of acetic acid over 30 minutes while stirring at room temperature. After completion of the dropwise addition, the mixture was heated to 50 ° C while stirring the mixture, and the reaction was carried out for 3 hours. After cooling to room temperature, toluene and water were added, and the mixture was thoroughly mixed, and then allowed to stand, and the aqueous layer was separated and removed. The toluene solution layer of the upper layer was washed with water three times, and then concentrated under reduced pressure to obtain a polyoxane (B-2) represented by the following formula (8).

[化8]

(2) Modulation of hardenable composition [Example 1 to Example 4 and Comparative Example 1]

The components shown in the following Table 1 were mixed under normal pressure at 25 ° C in the amounts shown in Table 1, and the curable compositions of Examples 1 to 4 and Comparative Example 1 were obtained. In addition, the details of each component in Table 1 are as follows.

C-1: a network of platinum and 1,3-divinyl-1,1,3,3-tetramethyldioxane Compound (the amount of platinum metal is 4% by mass)

D-1: diphenyl bis(dimethylvinyl nonyloxy) decane

D-2: phenyl tris(dimethylvinyl nonyloxy) decane

E-1: ethynylcyclohexanol

(3) Evaluation of hardenable composition

The curable compositions of Examples 1 to 4 and Comparative Example 1 were evaluated by the following methods (3-1) to (3-5). The evaluation results are shown in Table 1.

(3-1) Viscosity

The viscosity of the curable composition was measured at 25 ° C using an E-type viscometer.

(3-2) Moisture resistance (water vapor transmission rate)

A frame having a thickness of 1 mm was fixed on a flat plate of Teflon, and a curable composition was applied so as to be the height of the frame, and heated in a hot air circulating oven at 150 ° C for 5 hours, thereby producing a vertical length of 50 mm. Hardened material with a width of 50 mm and a height of 0.3 mm. The water vapor transmission rate was measured at 40 ° C under conditions of 100% RH using a PREMATRAN-W3/31 apparatus manufactured by MOCON.

(3-3) Crack resistance

The curable composition was injected into an LED package (surface mount type, top view type, and polyphthalamide (PPA) resin), and dried at 100 ° C for 1 hour to be hardened, followed by 150. After drying at ° C for 5 hours and hardening, 10 semiconductor light-emitting elements including a cured product (sealing material) were produced. The obtained semiconductor light-emitting elements are kept at a constant temperature In a wet tank (manufactured by ESPEC Corp., PL-3KP), it is stored at 85 ° C and 85% RH for 5 hours, and then a tabletop reflow soldering device is used. The company manufactures, STR-2010), and performs two reflow steps with a maximum temperature of 260 ° C and 10 seconds. For each of the ten semiconductor light-emitting elements, the presence or absence of peeling between the cured product after the reflow treatment and the encapsulating resin was observed with an optical microscope.

When none of the ten semiconductor light-emitting elements were peeled off, it was "A" (determined to be good), and the case where one or two semiconductor light-emitting elements which were peeled off was "B" (determined to be slightly better), In the case where three or more semiconductor light-emitting elements that have been peeled off are "C" (determined as defective).

(3-4) Refractive index

The cured product produced in the following hardness measurement application was measured for refractive index at 25 ° C using a Model 2010 total reflection refractometer manufactured by Metricon. In addition, the measurement wavelength was 408 nm.

(3-5) Hardness

A 2 mm-thick frame was fixed to the Teflon plate, and the curable composition was applied in such a manner as to be the height of the frame, and heated in a hot air circulating oven at 150 ° C for 5 hours to prepare a vertical 50 mm. Hardened material of 50 mm height and 1 mm height. The hardness of the cured product was measured using a D-type and a-type hardness tester prescribed in JIS K6253.

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.

1‧‧‧Optical semiconductor device

2‧‧‧Semiconductor light-emitting elements

3‧‧‧ reflector

4‧‧‧ Sealing material

5‧‧‧ particles

6‧‧‧Electrode

7‧‧‧Wire

Claims (5)

A curable composition comprising: a polyoxyalkylene (A) having at least two alkenyl groups represented by the following formula (1); and a polyoxyalkylene (B) represented by the following formula (2); And a catalyst for hydrogenation reaction (C), [Chem. 1] (R ¹ ₃ SiO _1/2 ) _a (R ^Ar1 ₂ SiO _2/2 ) _b (R ² ₂ SiO _2/2 ) _c (R ³ SiO _{3 / 2} ) _d (SiO _4/2 ) _e (XO _1/2 ) _f (1) (wherein R ¹ , R ² and R ³ each independently represent an alkyl group, an alkenyl group, an aryl group or a bonding group; , on the same silicon atom bonded to a 2 R ² wherein R ² is aryl, the other R ² is not an aryl group; and, all of the ^{R. 1,} at least R ² and R ³ is 2 Alkenyl; R ^Ar1 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; and b and d each independently represent 1 or more. Integer) (wherein R ⁴ each independently represents a monovalent hydrocarbon group; R ^Ar2 each independently represents an aryl group; and n represents an integer of 1 or more). The sclerosing composition according to claim 1, wherein The polyoxyalkylene (B) is a compound of n≧2 in the above formula (2). The curable composition according to claim 1 or 2, wherein the content of the polyoxyalkylene (B) is 10% by mass based on 100 parts by mass of the polyoxyalkylene (A). Parts ~ 100 parts by mass. A cured product obtained by hardening a curable composition according to any one of claims 1 to 3. An optical semiconductor device comprising: a semiconductor light emitting element; and a cured product according to item 4 of the patent application of the semiconductor light emitting element.