TWI582169B - 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.

In order to protect the semiconductor light-emitting element from moisture, dust, and the like, the semiconductor light-emitting element is sealed with a sealing material such as a transparent resin. In order to prevent light emitted from the semiconductor light-emitting element from being reflected at the interface between the semiconductor light-emitting element having a high refractive index of a semiconductor layer such as GaN or InGaN and the sealing material, light extraction efficiency (brightness) from the light-emitting surface of the semiconductor light-emitting element to the outside is improved. It is necessary to increase the refractive index of the sealing material (Patent Document 1).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-123769

However, if the refractive index of the sealing material is increased, the light extraction efficiency from the light-emitting surface of the semiconductor light-emitting element to the sealing material is improved, but if the refractive index of the sealing material is increased, the sealing material and an external substance such as air (refractive index of about 1.00) )of The refractive index difference becomes large, and light is reflected at the interface between the sealing material and the outside. Therefore, there is a limit to the method of increasing the brightness by increasing the refractive index of the sealing material.

An object of the present invention is to provide an optical semiconductor device excellent in luminance, a sealing material (cured material) used in the optical semiconductor device, and a curable composition for forming the cured product.

The present invention for achieving the above object is as follows.

[1] A curable composition comprising: a polyoxyalkylene (A) having an aryl group, a fluorine atom, and at least two or more alkenyl groups per molecule; and a polyoxyalkylene (B) having At least two or more alkenyl groups and aryl groups per molecule, and having no fluorine atom; hydrogen hydride oxane (C) having at least two or more hydrogen atoms bonded to a ruthenium atom per molecule; And a catalyst (D) for hydrogenation reaction.

[2] The curable composition according to the above [1], wherein the content ratio of the polyoxyalkylene (A) is based on the total of the polyoxyalkylene (A) and the polyoxyalkylene (B). It is 30% by weight to 90% by weight.

[3] The hardenable composition according to the above [1] or [2] wherein the polyfluorene oxide (A) has a bond with a ruthenium atom in a main chain of the polyoxyalkylene (A). Polyoxyalkylene of the group represented by the following formula (1): -R ¹ -CF ₃ (1)

(In the formula (1), R ¹ represents an alkanediyl group having 1 to 20 carbon atoms or a group obtained by substituting a hydrogen atom of the alkanediyl group with a fluorine atom).

[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 the cured product according to [4] above.

The curable composition of the present invention can form a cured product of an optical semiconductor device which is excellent in luminance when used as a sealing material or the like. The optical semiconductor device having the cured product formed of the curable composition of the present invention as a sealing material is excellent in luminance.

1‧‧‧Optical semiconductor device

2‧‧‧Semiconductor light-emitting elements

3‧‧‧ reflector

4‧‧‧ Sealing material

5‧‧‧ particles

6‧‧‧Electrode

7‧‧‧ line

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: polyoxyalkylene (A) having at least two or more alkenyl groups, aryl groups, and fluorine atoms per molecule; polyoxyalkylene (B) having 1 per 1 At least two or more alkenyl groups and aryl groups in the molecule, and having no fluorine atom; hydrogen hydride oxane (C) having at least two or more hydrogen atoms bonded to a ruthenium atom per molecule; Catalyst (D) for hydrogenation reaction.

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

Polyoxane (A)

The polyoxyalkylene (A) is a polyoxyalkylene having an aryl group, a fluorine atom, and at least two or more alkenyl groups per molecule. Both the polyoxyalkylene (A) and the polyoxyalkylene (B) are the main components of the present composition, and are hardened by hydrogenation reaction with a hydrogenated hydrazine (C) to form a main body of the cured product.

Examples of the alkenyl group which the polyoxyalkylene (A) has 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 ring. Hexyl group and the like. Among the alkenyl groups, a vinyl group, an allyl group and a hexenyl group are preferred.

When the amount of all Si atoms contained in the polyoxyalkylene (A) is set to 100 mol%, the content of the alkenyl group in the polyoxyalkylene (A) is preferably from 3 mol% to 50 mol%. %, more preferably 5 mol% to 40 mol%, and particularly preferably 10 mol% to 30 mol%. When the content of the alkenyl group is within the above range, the hydrazine hydrogenation reaction of the polyoxyalkylene oxide (A) and the polyoxyalkylene oxide (B) with the hydrogenated hydrazine (C) is appropriately carried out to obtain a cured product having high strength.

Examples of the aryl group which the polyoxyalkylene (A) has include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like. Among these aryl groups, a phenyl group is preferred. Since the polyoxyalkylene (A) has an aryl group, when the cured product obtained from the present composition is used as a sealing material for an LED, it exhibits characteristics of obtaining high luminance.

When the amount of all Si atoms contained in the polyoxyalkylene (A) is set to 100 mol%, the content of the aryl group contained in the polyoxyalkylene (A) is preferably from 30 mol% to 120. Moer%, more preferably 50% by mole to 110% by mole, and particularly preferably 70% by mole to 100% by mole. When the content of the aryl group is in the range of 30 mol% to 120 mol%, a cured product having high luminance and high refractive index is obtained from the composition.

The polyoxyalkylene (A) has a fluorine atom. In this respect, the polyoxyalkylene (A) is different from the polyoxyalkylene (B) described later.

When the amount of all Si atoms contained in the polyoxyalkylene (A) is set to 100 mol%, the content of the fluorine atom contained in the polyoxyalkylene (A) is preferably from 1 mol% to 60%. Moer%, more preferably 3 mol% to 40 mol%, and particularly preferably 5 mol% to 30 mol%. When the content of the fluorine atom is within the above range, when the cured product obtained from the present composition is used as a sealing material for an LED, high luminance is exhibited.

The polyoxyalkylene (A) is preferably a polyoxyalkylene having a group represented by the following formula (1) bonded to a ruthenium atom in the main chain of the polyoxyalkylene (A):- R ¹ -CF ₃ (1)

(In the formula (1), R ¹ represents an alkanediyl group having 1 to 20 carbon atoms or a group obtained by substituting a hydrogen atom of the alkanediyl group with a fluorine atom).

R ¹ is an alkanediyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, that is, an alkanediyl group having 1 to 20 carbon atoms or a group in which a hydrogen atom of the alkanediyl group is substituted with a fluorine atom. The carbon number of the alkanediyl group is more preferably from 2 to 8.

The method for producing the polyoxyalkylene (A) is, for example, a method in which an alkoxydecane having at least one alkenyl group, an aryl group, and a fluorine atom is used in an appropriate combination, and is disclosed in Japanese Laid-Open Patent Publication No. Hei 6-9659. Japanese Patent Laid-Open No. 2003-183582, Japanese Patent Laid-Open No. 2007-008996, and Japanese Patent Laid-Open A known method described in, for example, JP-A-2007- 169, 427, and JP-A-2010-059359, for example, a chlorodecane or an alkane having an alkenyl group or an aryl group as a unit A method in which oxydecane is co-hydrolyzed, or a method in which a co-hydrolyzate is subjected to an equilibrium reaction by an alkali metal catalyst or the like.

The alkoxy decane which has a fluorine atom is, for example, an alkoxy decane represented by the following formula (2).

In the formula (2), R ² is a fluoroalkyl group in which an alkyl group having 1 to 26 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, is partially or wholly substituted with a fluorine atom. R ³ is a divalent group, for example, -(CH ₂ ) _n - (n is an integer of 2 to 20), -(CH ₂ ) _n -X-(CH ₂ ) _P - (-X- is -O- or - C(O)O-, n is an integer from 0 to 2, p is an integer from 5 to 25), or -QS-(CH ₂ ) _q - (Q is a divalent group containing at least one oxygen atom, q is 2 or 3), R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and r is 0, 1, or 2.

The alkoxydecane may be exemplified by 3,3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, and 3,3,3-trifluoropropylmethyl. Dimethoxy decane, 3,3,3-trifluoropropyl dimethyl methoxy decane, 4,4,4-trifluorobutyltrimethoxy fluorene Alkane, 4,4,4-trifluorobutyltriethoxydecane, 3,3,4,4,4-pentafluorobutyltrimethoxydecane, 3,3,4,4,4-pentafluorobutane Triethoxy decane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltrimethoxydecane, 3,3,4,4 ,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxydecane, 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10,10-heptadecafluorodecyltrimethoxydecane, 3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10-heptadecafluorodecyltriethoxydecane, 15-(trifluoroethoxy)pentadecyl-15-(trifluoroacetoxy)pentadecylmethyldi Ethoxy decane and the like.

The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of polyoxyalkylene (A) is usually in the range of 100 to 50,000, 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 content of the polyoxyalkylene (A) in the present composition is preferably from 30% by weight to 90% by weight, and more preferably 50%, based on the total of the polyoxyalkylene (A) and the polyoxyalkylene (B). The weight % to 90% by weight, particularly preferably 60 to 85% by weight. When the content ratio of the polyoxyalkylene (A) is within the above range, when the cured product obtained from the present composition is used as a sealing material for an LED, high luminance is exhibited.

Polyoxane (B)

The polyoxyalkylene (B) is a polyoxyalkylene having at least two or more alkenyl groups and an aryl group per molecule and having no fluorine atom. Both the polyoxyalkylene (B) and the polyoxyalkylene (A) are the main components of the present composition, and are hardened by hydrogenation reaction with hydrazine hydride (C) to form a main body of the cured product.

The polyoxyalkylene (B) has an alkenyl group which is the same as the alkenyl group described in the polyoxyalkylene (A).

The polyoxyalkylene (B) has the same aryl group as described in the polyoxyalkylene (A).

The polyoxyalkylene (B) does not have a fluorine atom. In this respect, the polyoxyalkylene (B) is different from the above polyoxyalkylene (A).

The polystyrene-equivalent weight average molecular weight of the polyoxyalkylene (B) measured by gel permeation chromatography is usually in the range of 100 to 50,000, preferably 500 to 10,000. When the weight average molecular weight of the polyoxyalkylene (B) is within the above range, it is easy to handle the production of the sealing material using the composition, and the cured product obtained from the composition has sufficient strength as the optical semiconductor sealing material.

The polyoxyalkylene (B) can be suitably used in combination with an alkoxydecane having at least one alkenyl group, aryl group and fluorine atom, and can be produced by a known method in the same manner as the polyoxyalkylene (A).

Hydrogenated oxane (C)

The hydrogenated oxane (C) has at least two or more hydrogen atoms bonded to a ruthenium atom per molecule (hereinafter also referred to as a hydrogen bonded to a ruthenium atom). Hydrogenated oxane (C) is a cross-linking agent for polyoxyalkylene (A) and polyoxyalkylene (B), hydrogenated by hydrazine with polyoxyalkylene (A) and polyoxyalkylene (B) The reaction forms a hardened substance.

The hydrogenated oxane (C) is a polyoxane having a hydrogen atom bonded to at least two of the ruthenium atoms per molecule, as long as it is used as a crosslinking agent in the conventional hydroalkylene-based polyoxane composition. There is no particular limitation on the alkane.

The hydrogenated oxane (C) can be, for example, alkoxy decane such as phenyltrimethoxydecane or diphenyldimethoxydecane and 1,1,3,3-tetramethyldifluoride by a known method. A hydrogenated oxane such as oxane is obtained by a reaction in a suitable synthetic solvent.

The content of the hydrogenated hydrazine (C) in the curable composition of the present invention is preferably a total amount of the alkenyl group in the polysiloxane (A) and the polyoxyalkylene (B). The molar ratio of hydrogen bonded to the ruthenium atom in (C) is 0.1 to 5, more preferably 0.5 to 2, and particularly preferably 0.7 to 1.4. When the content of the hydroquinone (C) is within the above range, the curing of the composition proceeds sufficiently, and the obtained cured product has sufficient heat resistance.

Catalyst for hydrogenation reaction (D)

The catalyst for hydrogenation of hydrazine (D) is a catalyst for the hydrogenation reaction of polyoxyalkylene (A) and polyoxyalkylene (B) with hydrazine hydride (C).

The catalyst for hydrogenation reaction (D) can be used without particular limitation as long as it is used as a catalyst for hydrogenation reaction in a conventional hydroalkylene-based polyoxane composition.

Specific examples of the catalyst (D) for the hydrogenation reaction include a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. Among these catalysts, a platinum-based catalyst is preferred from the viewpoint of promoting the hardening of the composition. 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 complex, 1,3-divinyl-1,1,3,3-tetramethyldioxane is preferred.

The content of the catalyst (D) for the rhodium hydrogenation reaction in the curable composition of the present invention is a hydrogenation reaction of polyfluorene oxide (A) and polyoxyalkylene (B) with hydrogen hydride (C). The amount carried out in reality.

In addition to the above-mentioned components, the curable composition of the present invention may contain, for example, fine particles of cerium oxide such as fired cerium oxide or quartz powder, and inorganic fillers such as titanium oxide and zinc oxide. a retarder such as cyclotetramethyltetravinyltetraoxane, a diluent such as diphenyl bis(dimethylvinyl decyloxy) decane or phenyl tris(dimethylvinyl decyloxy) decane, Reaction inhibitors such as phosphors, pigments, flame retardants, heat-resistant agents, antioxidants, acetylene alcohols, and the like.

The curable composition of the present invention can be produced 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~1000000mPa. s, more preferably 10mPa. s~10000mPa. s. When the viscosity is within the above range, the workability of the composition is improved.

The curable composition of the present invention can be prepared into one type of solution, or can be prepared by dividing into two kinds of solutions, and two kinds of solutions are mixed and used at the time of use. A small amount of a hardening inhibitor such as acetylene alcohol may be added as needed.

Since the curable composition of the present invention contains a polysiloxane (A) having a fluorine atom and a polyoxyalkylene (B) having no fluorine atom, the curable composition of the present invention is applied to, for example, a substrate. Further, the coating film has a relatively large amount of polyoxyalkylene (A) having a fluorine atom on the air side due to the relationship between the surface tension and the polysiloxane (B) having no fluorine atom. Presumed as follows: by hardening the coating film, A cured product of a multilayer structure having a layer containing a large amount of fluorine atoms on the air side is obtained. That is, it is estimated that when the curable composition of the present invention is used, a cured product having a multilayer structure can be obtained by one coating step. Further, the multilayer structure has an effect of lowering the refractive index of the fluorine atom, and the closer to the air side layer, the lower the refractive index. Therefore, the difference in refractive index between the layer on the air side of the cured product and the air is small, and as a result, it is estimated that the optical semiconductor device having the cured product obtained from the curable composition of the present invention is excellent in brightness.

The method of repeating the coating step for forming each layer to obtain a cured product of a multilayer structure has problems in that (1) is complicated and costly; and (2) a composition for forming a second layer is coated on the first layer. In the case where the coating property is deteriorated depending on the surface tension of the composition, there is a possibility that a uniform coating film cannot be formed. In particular, since the composition containing fluorine is largely degraded by the surface tension of the liquid, there is a high possibility of rejection at the time of coating, and there is a possibility of foaming, which is a problem in this respect. The curable composition of the present invention is extremely excellent in that it is less likely to cause the above problems.

Further, in the conventional composition for forming a cured product having a multilayer structure, that is, a composition containing a component having a fluorine atom and a component having no fluorine atom, it is considered that after the formation of the cured product, the component containing fluorine exudes from the hardened material to the air. On the side, the following problems are expected: (1) insufficient hardenability and insufficient crack resistance of the cured product, and (2) insufficient gas barrier property of the cured product. On the other hand, the curable composition of the present application is extremely excellent in that it is less likely to cause such a problem.

<hardened matter>

The cured product is obtained by curing the curable composition of the present invention. If you use this The curable composition of the invention seals the semiconductor element and hardens it to obtain a cured product as a sealing material.

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

As described above, it is presumed that the cured product obtained by curing the curable composition of the present invention has a multilayer structure. In the cured product formed by applying and hardening the curable composition of the present invention onto a substrate, a component derived from polyoxyalkylene (A) and a component derived from polyoxyalkylene (B) are formed. The components contain a plurality of layers having different ratios. Specifically, it is considered that the content of the component derived from polyoxyalkylene (A) is low, and the first layer having a high content ratio of the component derived from polysiloxane (B) is formed on the substrate surface, and is derived from the polymerization. The second layer having a high content ratio of the component of the siloxane (A) and having a low content of the component derived from the polysiloxane (B) is formed on the first layer. That is, the concentration of fluorine atoms in the first layer formed on the substrate surface is low, and the concentration of fluorine atoms in the second layer formed on the first layer is high. Since the cured product of the present invention has the above-described plurality of layers, it is estimated that when the cured product is used as a sealing material for a semiconductor light-emitting element, an optical semiconductor device having high luminance is obtained.

<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 has a semiconductor light emitting element and the cured material covering the semiconductor light emitting element. The optical semiconductor device of the present invention is obtained by coating the above-mentioned curable composition on a semiconductor light-emitting device and curing 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 disposed on the electrode 6, and is electrically connected to the electrode 6 by a wire 7 and a reflector 3 for accommodating the semiconductor light emitting element 2 And a sealing material 4 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 optical semiconductor device having the cured product described above as a sealing material has high luminance.

[Examples]

1. Preparation of hardenable composition

1-1. Structural analysis

The structure of the synthesized compound was calculated by ²⁹ Si nuclear magnetic resonance (NMR) and ¹ H 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 equivalent value.

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

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

Dissolved solution: tetrahydrofuran (THF), flow rate 0.5 mL/min, loading 5.0%, 100μL

1-3. Synthesis of each component

The azide units listed below are represented by the following symbols: M(Vi): (ViMe ₂ SiO _1/2 )

M(H): (HMe ₂ SiO _1/2 )

D(Ph): (Ph ₂ SiO _2/2 )

D(PhMe): (PhMeSiO _2/2 )

D(Ep): (MeEpSiO _2/2 )

T(Ph): (PhSiO _3/2 )

T(F): (CF ₃ CH ₂ CH ₂ SiO _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 polyoxyalkylene (A1)

1,3-Divinyl-1,1,3,3-tetramethyldioxane 112g, phenyltrimethoxydecane 476g, diphenyldimethoxydecane 293g, trifluoroethylene were added to the reaction vessel. 262 g of propyltrimethoxydecane, 236 g of water, 0.9 g of trifluoromethanesulfonic acid and 460 g of toluene were heated under reflux for 1 hour. Then, 0.6 g of potassium hydroxide was added and refluxed for 5 hours. After neutralization with acetic acid, water washing was carried out to obtain a polyoxyalkylene (A1) containing 20 mol of M(Vi), 40 mol of T(Ph), 20 mol of D(Ph), and 20 mol of T(F). The polyoxyalkylene (A1) had a weight average molecular weight of 1,700.

[Synthesis Example 2] Synthesis of polyoxyalkylene (B1)

Add 1,3-divinyl-1,1,3,3-tetramethyldioxane 37.3 to the reactor g, 234 g of phenyltrimethoxydecane, 97.7 g of methylphenyldimethoxydecane, 55 g of water, 0.3 g of trifluoromethanesulfonic acid, and 146 g of toluene were heated under reflux for 1 hour. Then, 4.4 g of 3-glycidoxypropylmethyldimethoxydecane and 0.3 g of potassium hydroxide were added, and the mixture was heated under reflux for 5 hours. After neutralization with an acid, liquid separation extraction was carried out using toluene and water to obtain a polyoxyxane containing 20 mol of M(Vi), 59 mol of T(Ph), 20 mol of D(PhMe), and 1 mol of D(Ep). (B1). The polyoxyalkylene (B1) had a weight average molecular weight of 1,600.

[Synthesis Example 3] Synthesis of polyoxyalkylene (B2)

149 g of phenyltrimethoxydecane, 183 g of diphenyldimethoxydecane, 0.6 g of trifluoromethanesulfonic acid, and 1,3-divinyl-1,1,3,3-tetramethyl were added to the reaction vessel. 653 g of dioxane, and then 40 g of acetic acid was added, and then heated at 50 ° C for 3 hours. After heating, liquid separation extraction was carried out using toluene and water to obtain polysiloxane (B2) containing 70 mol of M(Vi), 15 mol of T(Ph), and 15 mol of D(Ph). The polyoxyalkylene (B2) has a weight average molecular weight of 500.

[Synthesis Example 4] Synthesis of polyoxyalkylene (B3)

In the reaction vessel, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane, 525 g of phenyltrimethoxydecane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid, and toluene were added. 500 g, heated to reflux for 1 hour. Then, 314 g of 3-glycidoxypropylmethyldimethoxydecane, 130 g of water, and 0.5 g of potassium hydroxide were added, and the mixture was heated under reflux for 1 hour. After neutralizing with an acid, liquid separation extraction was carried out using toluene and water to obtain a polyoxyalkylene (B3) containing 25 mol of M(Vi), 75 mol of T(Ph), and 40 mol of D(Ep). The polyoxyalkylene (B3) had a weight average molecular weight of 2,800.

[Synthesis Example 5] Synthesis of polyoxyalkylene (C1)

220 g of diphenyl dimethoxy decane, 0.6 g of trifluoromethanesulfonic acid, and 60.5 g of 1,1,3,3-tetramethyldioxane were added to the reaction vessel, and 30 while stirring at room temperature. 108 g of acetic acid was added dropwise in a minute. After completion of the dropwise addition, the mixture was heated at 50 ° C for 3 hours while stirring, and then heated at 80 ° C for 2 hours. After heating, liquid separation extraction was carried out using toluene and water to obtain a polyoxyalkylene (C1) represented by the following formula (3).

[Synthesis Example 6] Synthesis of polyoxyalkylene (C2)

40 g of phenyltrimethoxydecane, 0.06 g of trifluoromethanesulfonic acid, and 20.3 g of 1,1,3,3-tetramethyldioxane were added to the reaction vessel, and the mixture was stirred for 30 minutes while stirring at room temperature. Add acetic acid 54g. After completion of the dropwise addition, the mixture was heated at 50 ° C for 3 hours while stirring. After heating, liquid separation extraction was carried out using toluene and water to obtain a polyoxyalkylene (C2) containing 60 mol of M(H) and 40 mol of T(Ph). The polyoxyalkylene (C2) has a weight average molecular weight of 800.

2. Preparation of hardenable composition

[Example 1 to Example 6, 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 6 and Comparative Examples 1 to 3 were obtained. The "parts" in Table 1 represent parts by mass. Further, the molar ratio of the hydrogen atom of the bonded ruthenium atom in the compound (A) to the alkenyl group in the polyoxyalkylene (B) was 1.05. In addition, the details of each component in Table 1 are as follows.

Reaction catalyst for hydrogenation of hydrazine (D1): a complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldioxane (the amount of platinum metal is 4% by mass)

Compound (E1): ethynylcyclohexanol

Compound (E2): 3-methyl-1-butyn-3-ol

Compound (E3): 3,5-dimethyl-1-hexyn-3-ol

3. Evaluation of hardening composition

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

3-1. Brightness increase rate

The curable composition is applied to a surface mount type (a plan view including a portion including the semiconductor light-emitting device 2, the electrode 6, the wire 7, and the reflector 3 of FIG. 1) of the optical semiconductor at 150 ° C. The sample for evaluation was prepared by heating for 1 hour.

The radiant flux measurement of the above-mentioned evaluation sample was carried out using a total radiant flux measuring device (intensified multichannel photodetector MCPD-3700, Φ300 mm integrating sphere (hemispherical integrating sphere)). The ratio of the radiant flux of the sample for evaluation to the initial radiant flux measured by energization of the package before application of the sealing material to the radiant flux, and the radiation of the curable composition according to Comparative Example 1 was calculated in %. The rate of increase in the ratio of flux is evaluated.

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

Note the hardenable composition obtained in the above "2. Preparation of curable composition" The LED package (surface mount type, top view type) was heated at 100 ° C for 1 hour, and then heated at 150 ° C for 5 hours to prepare 10 samples in which a cured product was formed in the LED package (hereinafter referred to as Sample 1) for evaluation. The obtained sample for evaluation 1 was placed in a constant temperature and humidity chamber (manufactured by Espec, trade name "PL-3KP"), and kept in an environment of 85 ° C and 85% RH for 8 hours, and then used. A solder reflow device (manufactured by Senju Metal Industry Co., Ltd., trade name "STR-2010") was heated at 260 ° C for 20 seconds (high temperature and high humidity test). The presence or absence of cracks of the cured product after the high-temperature and high-humidity test was observed by an optical microscope, and the crack resistance after the high-temperature and high-humidity test was evaluated. The evaluation was performed on the basis of the following criteria.

A: No cracks were observed on any of the 10 samples.

B: One to four samples of 10 samples had cracks.

C: There were cracks on more than 5 of the 10 samples.

3-3. Gas barrier to hydrogen sulfide

The curable composition obtained in the above "2. Preparation of a curable composition" was injected into an LED package (surface mount type, plan view type), and heated at 100 ° C for 1 hour, followed by heating at 150 ° C for 5 hours. A sample in which a cured product was formed in the LED package (hereinafter referred to as sample for evaluation 2) was prepared. The sample for evaluation 2 was placed in a heating vessel filled with a gas containing 90% by volume of air and 10% by volume of hydrogen sulfide, and the sample for evaluation 2 was heated at 80 ° C for 24 hours. The appearance of the silver electrode of the LED package of the sample 2 for evaluation before and after heating was observed with 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 in the silver electrode before and after heating.

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

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

3-4. Hardness

A 2 mm-thick frame was placed on a Teflon plate, and the curable composition obtained in the above "2. Preparation of a curable composition" was applied to the height of the frame, and the hot air circulation was performed at 150 ° C. The mixture was heated in an oven for 5 hours to prepare a cured product having a length of 5 mm, a width of 5 mm, and a height of 1 mm. The hardness of the cured product was measured using a D-type hardness tester specified in JIS K6253.

3-5. Viscosity

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

1‧‧‧Optical semiconductor device

2‧‧‧Semiconductor light-emitting elements

3‧‧‧ reflector

4‧‧‧ Sealing material

5‧‧‧ particles

6‧‧‧Electrode

7‧‧‧ line

Claims (4)

A curable composition comprising: a polyoxyalkylene (A) having an aryl group, a fluorine atom, and at least two or more alkenyl groups per molecule; and a polyoxyalkylene (B) having one molecule per molecule At least two or more alkenyl groups and aryl groups, and having no fluorine atom; hydrogen hydride oxane (C) having at least two or more hydrogen atoms bonded to a ruthenium atom per molecule; The reaction catalyst (D) is contained in an amount of 30% by weight to 90% by weight based on the total of the polyoxyalkylene oxide (A) and the polyoxyalkylene oxide (B). . The curable composition according to claim 1, wherein the polyoxyalkylene (A) is a compound having the following formula (1) bonded to a ruthenium atom in the main chain of the polyoxyalkylene (A). a polyoxyalkylene group represented by a group: -R ¹ -CF ₃ (1) In the formula (1), R ¹ represents an alkanediyl group having 1 to 20 carbon atoms or a hydrogen atom of the alkanediyl group is fluorine A group substituted by an atom. A cured product obtained by curing the curable composition according to any one of the first to second aspects of the invention. An optical semiconductor device having a cured product as described in claim 3 of the patent application.