TW201533227A - Curable composition for sealing photo-semiconductor and photo-semiconductor device using same - Google Patents

Abstract

To provide curable composition for sealing photo-semiconductor endowed with the excellent impact resistance and anti-cracking property and containing the curing product of low gas permeability, and the photo-semiconductor device obtained by the photo-semiconductor element sealed by the curing product obtained by means of making the curable composition for sealing photo-semiconductor hardened. The curable composition for sealing photo-semiconductor is to comprise (A) the linear multi-fluorine compound containing above two vinyl groups in one molecule and perfluorine polyether structure in the main chain, (B) the organic hydrogen polysiloxane as shown by the below-mentioned general formula (1), (C) the catalyst of platinum family, (D) the cyclic organic polysiloxane as shown by the below-mentioned general formula (2), and (E) the carboxylic anhydride, wherein the hardness of curing product obtained by hardening the curable composition for sealing photo-semiconductor is 30-90 measured by the A-type rubber Durometer according to the standard of JIS K6253-3:2012.

Description

Curable composition for optical semiconductor sealing and optical semiconductor device using the same

The present invention relates to a curable composition for sealing an optical semiconductor and an optical semiconductor device using the same.

Conventionally, as a curable composition, a linear fluoropolyether compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain has been proposed, and two or more of them have one molecule. a composition obtained by directly bonding a fluorine-containing organic hydrogen polyoxane and a platinum group compound of a hydrogen atom of a halogen atom to obtain heat resistance, chemical resistance, solvent resistance, mold release property, water repellency, oil repellency, An excellent cured product having a good balance of properties such as low-temperature characteristics (Patent Document 1).

Further, a composition in which a self-adhesive property is imparted to a metal or a plastic substrate by adding an organopolysiloxane having a hydroquinone group and an epoxy group and/or a trialkoxyalkyl group is proposed. (Patent Document 2).

Further, there has been proposed a composition for improving the adhesion to various substrates, particularly polyphenylene sulfide (PPS) or polyamide resin, by adding a carboxylic anhydride to the above composition (Patent Document 3). Also, patent In the fourth aspect, a composition capable of preventing a decrease in luminance even in the presence of a corrosive acid gas or an alkaline gas has been proposed.

However, in the hardened material obtained by hardening the composition actually prepared in the prior art, the hardness of the type A durometer specified in JIS K6253-3:2012 is as low as about 20, and is used as the light-emitting two. In the case of a sealing material of a polar body (hereinafter referred to as "LED"), the impact resistance of the sealing material may be insufficient. For example, when the optical semiconductor device in which the LED is stacked in the hardened material is used, and the bowl type vibrating parts feeder is arranged in a certain direction/posture, the optical semiconductor devices collide with each other. The impact causes the problem of disconnecting the bonding wires connecting the LED chips and the electrodes.

On the other hand, when the optical semiconductor device in which the LED is sealed with the cured product having a hardness of 90 or more of the A-type rubber hardness meter is subjected to a temperature cycle test, cracking may occur in the cured product.

Further, in the optical semiconductor device in which the LED is sealed, in order to improve the brightness, silver may be plated around the LED. The optical semiconductor device using a cured product obtained by hardening a composition prepared by the above prior art as a sealing material for an LED is used in an environment exposed to a sulfur-based gas, and the sulfur-based gas penetrates due to passage of time. This hardened material discolors silver into black, so that the brightness is often lowered. Therefore, as such a composition, when it is hardened to be a cured product, it is required to exhibit a lower gas permeability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-199070

[Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 9-095615

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-072868

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-277887

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable composition for optical semiconductor sealing which provides a cured product having excellent impact resistance and crack resistance and having low gas permeability, and The cured product obtained by curing the curable composition for optical semiconductor sealing is used to seal the optical semiconductor device of the optical semiconductor element.

In order to solve the above problems, the present invention provides a curable composition for optical semiconductor sealing, which comprises (A) one molecule having two or more alkenyl groups, a main chain further having a perfluoropolyether structure, and an alkenyl group. A linear polyfluorinated compound having a content of 0.0050 to 0.200 mol/100 g: 100 parts by mass, (B) an organohydrogen polyoxyalkylene represented by the following formula (1), [Chemical 1] (wherein, a is an integer of from 3 to 10, and A is a divalent organic group containing a perfluoroalkylene group, a perfluoroalkylalkylene group, or both thereof, and D is independently of each other and may contain a halogen atom, oxygen a substituted or unsubstituted divalent hydrocarbon group of an atom or a nitrogen atom, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and R ² is independently a hydrogen atom or may contain a halogen atom or an oxygen atom. Or a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom by a divalent hydrocarbon group of a nitrogen atom, and three or more of R ² are a hydrogen atom).

(C) a platinum group metal catalyst: 0.1 to 500 ppm in terms of a platinum group metal atom, and (D) a cyclic organopolyoxane represented by the following formula (2): 0.10 to 10.0 parts by mass, (wherein b is an integer from 1 to 6, c is an integer from 1 to 4, d is an integer from 1 to 4, b+c+d is an integer from 4 to 10, and R ³ is independently substituted or not The substituted monovalent hydrocarbon group, which is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom. Further, G is independently an epoxy group or a trialkoxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain an oxygen atom, or both. However, -(SiO)(H)R ³ -, - (SiO) (E) R ³ -, and - (SiO) (G) R ³ - bonding order is not limited).

(E) carboxylic anhydride: 0.010 to 10.0 parts by mass

The curable composition for sealing a light semiconductor, wherein the blending amount of the component (B) is directly bonded to the component (B) with respect to the alkenyl group 1 mol contained in the composition. The hardness of the hardened material obtained by curing the photo-semiconductor sealing hardenable material is 0.50 to 2.0 mol, and the A-type rubber hardness meter specified in JIS K6253-3:2012 is The value of 30~90.

In the case of the curable composition for optical semiconductor sealing which contains all of the above-mentioned (A) to (E) components and the hardness of the cured product has the above-described range of the addition-curable fluoropolyether-based curable composition, A hardened material that is excellent in impact resistance and crack resistance and has low gas permeability.

Further, it is preferred to contain 0.10 to 50.0 parts by mass of the cyclic organopolysiloxane represented by the following formula (3) as the component (F).

(wherein e is an integer from 1 to 4, f is an integer from 3 to 6, e+f is an integer from 4 to 10, and R ⁴ is independently substituted or unsubstituted monovalent hydrocarbon group, and J is independent of each other The ground is a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom, and the L system is independently bonded directly to each other. The alkenyl group of the ruthenium atom. However, the order of bonding of -(SiO)(J)R ⁴ - and -(SiO)(L)R ⁴ - is not limited).

In the case of the curable composition for optical semiconductor sealing containing the component (A) and the component (F) as described above, the impact resistance and the crack resistance are more excellent. And has a low gas permeability hardened material. Therefore, the cured product of the curable composition for optical semiconductor sealing can be suitably used for a sealing material for an optical semiconductor element, particularly a sealing material for protecting an LED.

Further, the component (A) is preferably a linear polyfluoro compound represented by the following formula (4).

(wherein R ⁶ and R ⁷ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and one or more of them are alkenyl groups. R ⁸ is independently a hydrogen atom, or a substituted or unsubstituted one. The monovalent hydrocarbon group, g and h are each an integer from 1 to 150, and the average value of g+h is 2 to 300, and i is an integer of 0 to 6).

Furthermore, it is preferable that the component (A) is one or more types selected from the group consisting of the following general formula (5), the following general formula (6), and the following general formula (7). Fluorine compound.

(wherein R ⁸ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and g and h are each an integer of from 1 to 150, and an average value of g + h is from 2 to 300, i is An integer of 0 to 6, R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other.

(wherein R ⁸ , R ⁹ , g, h, and i are the same as described above).

(wherein R ⁸ , g, h, and i are the same as described above).

When it is such a component (A), heat resistance, chemical resistance, solvent resistance, mold release property, water repellency, oil repellency, low temperature property, etc. are obtained. The property is well balanced and is a more excellent hardened material for the sealing material.

In addition, the perfluoroalkylalkylene group contained in the component (B) preferably contains 1 to 500 groups of repeating units represented by the following formula (8).

-C _e' F _2e' O- (8) (wherein e' is independently an integer from 1 to 6 per unit).

Further, A of the component (B) is preferably selected from the group consisting of the following general formula (9), the following general formula (10), and the following general formula (11).

(wherein R ¹⁰ is independently a fluorine atom or a CF ₃ group, j is an integer of 1 to 4, and k and n are each an integer of 0 to 200, and an average value of k + n is 0 to 400, and l is An integer from 2 to 6. In addition, the order of bonding of each repeating unit is not limited).

(wherein p is an integer from 1 to 200, and j is the same as above).

(In the formula, R ¹⁰ , j, k, and n are the same as described above. Further, the order of bonding of each repeating unit is not limited).

If it is such a component (B), a cured product having lower gas permeability can be obtained.

Further, the component (E) is preferably a carboxylic anhydride selected from the group consisting of the following general formula (12) and the following general formula (13).

(wherein q is an integer from 1 to 6, r is an integer from 1 to 4, s is an integer from 1 to 4, q+r+s is an integer from 4 to 10, and R ¹¹ is independently substituted or not The substituted monovalent hydrocarbon group, which is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom. And Q is a cyclic carboxylic acid anhydride residue which is bonded to a ruthenium atom via a divalent hydrocarbon group independently of each other. However, -(SiO)(H)R ¹¹ -, -(SiO)(M)R ¹¹ - and - (SiO) (Q) R ¹¹ - The bonding sequence is not limited).

【化12】 (In the formula, R ¹¹ , M, and Q are the same as described above, t is an integer of 1 to 3, _u is an integer of 0 to 2, and t + u is 3).

According to the component (E), a cured product having improved adhesion to various substrates can be obtained.

Further, the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group is preferably a group represented by the following formula (14) or formula (15) independently of each other.

C _v F _2v+1 - (14) (where v is an integer from 1 to 10).

(where w is an integer from 1 to 10).

When it is such a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, it is a composition which is more excellent in compatibility with the (A) component, dispersibility, and uniformity after hardening.

Further, the water vapor transmission rate of the cured product having a thickness of 1 mm obtained by curing the curable composition for optical semiconductor sealing is preferably 15.0 g/m ² . Below day.

Thus, the water vapor transmission rate is 15.0 g/m ² . In the case of using a cured product obtained by curing the composition of the present invention as a sealing material for an LED in an optical semiconductor device in which silver is coated around the LED, no silver is exposed to the sulfur-based gas. It is preferred to reduce the brightness.

Further, the curable composition for optical semiconductor sealing has a viscosity of 23 ° C as defined in JIS K7117-1:1999, preferably 50.0 to 50,000 mPa‧s.

Thus, the viscosity is 50.0 mPa. Above s, the no-flowing property is too high, and it is preferable to pott a certain amount of the dispenser in the LED package, so it is preferable; if it is 50,000 mPa. In the case where the curable composition for optical semiconductor sealing is filled in the LED package, it is not necessary to adjust the time, and the productivity is lowered, which is preferable.

Further, the cured product obtained by curing the curable composition for optical semiconductor sealing has a refractive index of preferably 1.30 or more and less than 1.40 at 25 ° C and 589 nm (line of sodium).

When the refractive index is 1.30 or more and less than 1.40, the optical semiconductor device obtained by sealing the LED by the cured product obtained by curing the composition of the present invention extracts the light emitted from the LED to the outside. It is better if the efficiency does not become insufficient.

Moreover, the present invention provides an optical semiconductor device comprising an optical semiconductor element and a cured product obtained by curing the optical semiconductor element for curing the curable composition for optical semiconductor sealing.

The curable composition for sealing an optical semiconductor according to the present invention is excellent in impact resistance and crack resistance, and has a low gas permeability and a cured product. Therefore, the light obtained by sealing the optical semiconductor element with the cured product is obtained. In the semiconductor device, even if the optical semiconductor device collides with each other, damage of the member is less likely to occur, so that yield and productivity can be improved. Moreover, even if the temperature cycle test is performed, cracking of the cured product is not easily caused, so that reliability can be improved. Further, since the sulfur-based gas does not easily penetrate the cured product, the decrease in brightness can be suppressed.

Further, the optical semiconductor element is preferably a light emitting diode.

In this way, the cured product of the curable composition for optical semiconductor sealing of the present invention can be suitably used as a sealing material for protecting the light-emitting diode.

In the curable composition for sealing an optical semiconductor of the present invention, by combining the above components (A) to (E) and further (F), the cured product has excellent impact resistance and crack resistance, and further Since it has low gas permeability, the optical semiconductor device obtained by sealing the optical semiconductor element with the cured product can be manufactured without causing damage to the member such as disconnection of the bonding wire. Further, even if the temperature cycle test is performed, the occurrence of cracks in the cured product can be suppressed. Further, even if the optical semiconductor device is used in an environment exposed to a sulfur-based gas, the reduction in brightness can be suppressed, and therefore it is suitable as a sealing material for protecting the LED.

1‧‧‧LED chip

2‧‧‧First lead frame

2a‧‧‧The front end of the first lead frame

2b‧‧‧ Terminal part of the first lead frame

2'‧‧‧ recess

3‧‧‧Second lead frame

3a‧‧‧ front end of the second lead frame

3b‧‧‧ Terminal part of the second lead frame

4‧‧‧ Bonding leads

5‧‧‧ Sealing material

6‧‧‧ convex lens

7‧‧‧Transparent resin department

8‧‧‧Package substrate

8’‧‧‧ recess

9‧‧‧Electrode

10, 10'‧‧‧Optical semiconductor devices

Fig. 1 is a schematic cross-sectional view showing an example of an optical semiconductor device of the present invention.

Fig. 2 is a schematic cross-sectional view showing another example of the optical semiconductor device of the present invention.

The invention is described in more detail below.

As described above, the curable composition for optical semiconductor sealing having excellent impact resistance and crack resistance, and further having low gas permeability, and the cured product obtained by curing the composition to seal the optical semiconductor Optical semiconductor devices derived from components are required.

As a result of intensive studies to achieve the above object, the present inventors have found that a composition containing the following components (A) to (E) and, if necessary, the component (F), is imparted with good resistance. The present invention has been completed in a curable composition for optical semiconductor sealing of a cured product having impact resistance and crack resistance and having low gas permeability.

Hereinafter, the present invention will be described in detail. In the present specification, the numerical range expressed by "~" means a range including numerical values described before and after "~" which is a lower limit and an upper limit.

[(A) ingredient]

The component (A) of the present invention is a linear polyfluoro compound having two or more alkenyl groups in one molecule, a perfluoropolyether structure in the main chain, and an alkenyl group content of 0.0050 to 0.200 mol/100 g. .

The alkenyl group contained in the component (A) is preferably a carbon number of 2 to 8, particularly preferably a carbon number of 2 to 6, and preferably has a CH ₂ =CH- structure at the terminal, and examples thereof include a vinyl group and an alkene. A propyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group or the like, and particularly preferably a vinyl group or an allyl group.

The perfluoropolyether structure contained in the component (A) is preferably a divalent perfluoropolyether group represented by the following formula (16) or the following formula (17).

In the above formula (16), x is 2 or 3, and y and a' are each preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and the average value of y+a' is preferably 2 ~300, more preferably 5~200, z is preferably an integer of 0~6, more preferably an integer of 0~4.

Further, in the above formula (17), b' is preferably 2 or 3, c' is preferably an integer of 1 to 300, more preferably an integer of 1 to 200, and d' is preferably an integer of 1 to 80. More preferably an integer from 1 to 50, and the average of c'+d' is Good for 2~380, better for 2~250.

The alkenyl group content in the component (A) is 0.0050 to 0.200 mol/100 g, preferably 0.0080 to 0.150 mol/100 g. When the alkenyl group content is less than 0.0050 mol/100 g, the degree of crosslinking becomes insufficient, and hardening failure occurs. When the alkenyl group content exceeds 0.200 mol/100 g, the mechanical properties of the cured product as a rubber elastomer may be impaired.

A preferred example of the component (A) is a linear polyfluoro compound represented by the following formula (4).

(wherein R ⁶ and R ⁷ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and one or more of them are alkenyl groups. R ⁸ is independently a hydrogen atom, or a substituted or unsubstituted one. The monovalent hydrocarbon group, g and h are each an integer from 1 to 150, and the average value of g+h is 2 to 300, and i is an integer of 0 to 6).

Here, the alkenyl group contained in R ⁶ and R ⁷ may be the same as the above, and the substituted or unsubstituted monovalent hydrocarbon group other than the above may preferably be a carbon number of 1 to 12, particularly preferably carbon. The number of 1 to 10, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group or an octyl group; an aryl group such as a phenyl group or a tolyl group; a benzyl group and a benzene group; An aralkyl group such as a benzyl group or the like, or a monovalent hydrocarbon group in which one or all of the hydrogen atoms of the group are substituted with a halogen atom such as fluorine. Among them, methyl and ethyl are particularly preferred.

The substituted or unsubstituted monovalent hydrocarbon group contained in R ⁸ may be the same as those exemplified as the substituted or unsubstituted monovalent hydrocarbon group of the above R ⁶ and R ⁷ .

Further, g and h are each preferably an integer of from 1 to 150, more preferably an integer of from 1 to 100, and the average value of g+h is preferably from 2 to 300, more preferably from 2 to 200. Further, i is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

A more preferable example of the component (A) is a linear polyfluoro compound represented by the following general formulae (5) to (7).

In the above formulae (5) to (7), R ⁸ is the same as the above, and g, h and i are the same as described above. Further, R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and examples thereof include the same as the substituted or unsubstituted monovalent hydrocarbon group of the above R ⁶ .

Specific examples of the linear polyfluoro compound represented by the above formula (5) include the following compounds. Hereinafter, Me represents a methyl group, and Et represents an ethyl group.

(wherein g and h are the same as described above).

Further, specific examples of the linear polyfluoro compound represented by the above formula (6) include the following formulas.

(wherein g and h are the same as described above).

Further, specific examples of the linear polyfluoro compound represented by the above formula (7) include the following formulas.

(wherein g and h are the same as described above).

Further, in order to use the composition of the present invention as a sealing material for an LED, the viscosity of the component (A) at 23 ° C is preferably 500 to 100,000 mPa as determined by JIS K7117-1:1999. s, more preferably 1,000 to 50,000 mPa. Within the scope of s.

The linear polyfluorinated compound of the above-mentioned (A) component may be used alone or in combination of two or more. In other words, one type of the linear polyfluoro compound represented by the above-mentioned general formulae (5) to (7) may be used alone or in combination of two or more.

[(B) ingredients]

The component (B) is an organohydrogenpolyoxyalkylene represented by the following formula (1), which functions as a crosslinking agent of the component (A). Also, the component (B) It contributes to the low gas permeability of the cured product obtained by hardening the composition of the present invention.

(wherein, a is an integer of from 3 to 10, and A is a divalent organic group containing a perfluoroalkylene group, a perfluoroalkylalkylene group, or both thereof, and D is independently of each other and may contain a halogen atom, oxygen a substituted or unsubstituted divalent hydrocarbon group of an atom or a nitrogen atom, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and R ² is independently a hydrogen atom or may contain a halogen atom or an oxygen atom. Or a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom by a divalent hydrocarbon group of a nitrogen atom, and three or more of R ² are a hydrogen atom).

In the above formula (1), a is an integer of from 3 to 10, preferably an integer of from 3 to 6.

Further, A is a perfluoroalkylene group, a perfluoroalkylalkylene group, or a divalent organic group containing both of them. Examples of the perfluoroalkylene group include a group represented by the following formula (8'). .

-C _m F _2m - (8') (wherein m is preferably an integer of 1 to 10, more preferably an integer of 1 to 5).

On the other hand, the perfluoroalkylalkylene group preferably has from 1 to 500, more preferably from 2 to 300, more preferably from 5 to 200, of the following formula (8): -C _e' F _2e' O- (8) (wherein e' is independently an integer from 1 to 6 per unit)

Represents the repeating unit.

Further, e' may be an integer of 1 to 6 different from each repeating unit, preferably an integer of 1 to 4.

Specific examples of the repeating unit represented by the above formula (8) include -CF ₂ O-, -CF ₂ CF ₂ O-, -CF ₂ CF ₂ CF ₂ O-, -CF(CF ₃ )CF ₂ O- -CF ₂ CF ₂ CF ₂ CF ₂ O-, -CF(CF ₃ )CF(CF ₃ )O-, and the like. Further, the perfluoroalkylalkylene group may be composed of one type of the above-mentioned repeating unit or a combination of two or more types.

A composed of the perfluoroalkylene group represented by the above formula (8') and the perfluoroalkylalkylene group represented by the above formula (8) is preferably represented by the following formulas (9) to (11). The 2 price base.

(wherein R ¹⁰ is independently a fluorine atom or a CF ₃ group, j is an integer of 1 to 4, and k and n are each an integer of 0 to 200, and an average value of k + n is 0 to 400, and l is An integer from 2 to 6. In addition, the order of bonding of each repeating unit is not limited).

(wherein p is an integer from 1 to 200, and j is the same as above).

(In the formula, R ¹⁰ , j, k, and n are the same as described above. Further, the order of bonding of each repeating unit is not limited).

In the above formula (9), R ¹⁰ is independently a fluorine atom or a CF ₃ group, j is an integer of 1 to 4, preferably 1 to 3, and k and n are each an integer of 0 to 200, preferably The average value of k+n is from 0 to 400, preferably from 2 to 300, and l is an integer from 2 to 6, preferably from 2 to 5. However, the bonding order of each repeating unit in the above formula (9) is not limited.

In the above formula (10), p is an integer of from 1 to 200, preferably An integer from 1 to 150, j is the same as above.

Further, in the above formula (11), R ¹⁰ , j, k and n are the same as described above. However, the bonding order of each repeating unit in the above formula (11) is not limited.

In the above formula (1), D is independently a substituted or unsubstituted divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom, and specifically, a stretching of 2 to 12 carbon atoms is exemplified. a group in which an alkyl group or a hydrogen atom of the alkylene group is substituted with a halogen atom such as fluorine, or an ether bond, an ester bond, a guanamine bond or a divalent aromatic hydrocarbon group is present in the alkyl group. . Specifically, the bases shown below can be exemplified. Further, among the following groups, it is preferred that the left side is bonded to the A bond and the right side is bonded to the ruthenium atom.

【化28】

Further, in the above formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and examples of the substituted or unsubstituted monovalent hydrocarbon group of the above R ⁶ , R ⁷ and R ⁸ are exemplified. The same base.

Further, in the above formula (1), R ² is independently a hydrogen atom or a monovalent perfluoroalkane bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a ruthenium atom, an oxygen atom or a nitrogen atom. Or a monovalent perfluorooxyalkyl group, and three or more of all R ² shown in the formula are a hydrogen atom.

Examples of the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group include the groups represented by the following formulas (14) and (15).

C _v F _2v+1 - (14) (wherein v is an integer of 1 to 10, preferably an integer of 3 to 7).

(wherein w is an integer of 1 to 10, preferably an integer of 2 to 8).

Further, a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom, which is a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group and a halogen atom, may be an alkylene group having 2 to 12 carbon atoms; Further, an ether bond, a ruthenium atom, a guanamine bond, a divalent aromatic hydrocarbon group, a carbonyl bond or the like may be present in the middle of the group, and specific examples thereof include the groups shown below.

As such a component (B), for example, a compound represented by the following formula can be exemplified. Further, k and n in the formula are the same as described above.

【化31】

【化32】

【化33】

The component (B) may be used alone or in combination of two or more. The blending amount of the above component (B) is a hydrogen atom (SiH group) of a halogen atom directly bonded to the component (B) with respect to the alkenyl group 1 mole contained in the composition of the present invention. It becomes 0.50~2.0 moules, and more preferably becomes 0.70~1.6 moules. When the SiH group is less than 0.50 mol, the degree of crosslinking is insufficient. On the other hand, when it is more than 2.0 mol, the storage property or the physical properties of the cured product obtained after curing may be impaired.

[(C) ingredient]

The platinum group metal catalyst of the component (C) of the present invention is a hydroquinone alkylation reaction catalyst. The hydroquinone alkylation reaction catalyst promotes an alkenyl group contained in the composition, particularly an alkenyl group in the component (A) and an alkenyl group (F) component, and a composition thereof. A catalyst for the addition reaction of the SiH group in the SiH group and the (B) component. The hydroquinone alkylation reaction catalyst is generally a noble metal or a compound thereof, and a platinum or platinum compound which is relatively easy to obtain is often used at a high price.

Examples of the platinum compound include a complex of chloroplatinic acid or chloroplatinic acid and an olefin such as ethylene, a complex with an alcohol or a vinyl siloxane, and a carrier of cerium oxide, aluminum oxide, carbon, or the like. Metal platinum, etc. As the platinum group metal catalyst other than platinum or a compound thereof, ruthenium, rhodium, iridium, and palladium compounds are also known, and examples thereof include RhCl(PPh ₃ ) ₃ , RhCl(CO)(PPh ₃ ) ₂ , and Ru _{3 .} (CO) ₁₂ , IrCl(CO)(PPh ₃ ) ₂ , Pd(PPh ₃ ) ₄ and the like. Further, in the above formula, Ph represents a phenyl group.

When such a catalyst is used, it can be used as a solid catalyst. However, in order to obtain a more uniform cured product, it is preferred to dissolve chloroplatinic acid or a complex compound in, for example, toluene or A suitable solvent such as ethanol is used in combination with a linear polyfluoro compound of the component (A).

The blending amount of the component (C) is an effective amount of the hydroquinone alkylation reaction catalyst, and is 0.1 to 500 ppm, particularly preferably 0.5 to 200 ppm, based on 100 parts by mass of the component (A). The atomic mass is converted, but it can be appropriately increased or decreased according to the desired hardening speed.

[(D) ingredient]

The component (D) of the present invention is a cyclic organopolyoxane represented by the following formula (2), which has a self-adhesive property imparted to the cured product obtained by curing the composition of the present invention. Features.

(wherein b is an integer from 1 to 6, c is an integer from 1 to 4, d is an integer from 1 to 4, b+c+d is an integer from 4 to 10, and R ³ is independently substituted or not The substituted monovalent hydrocarbon group, which is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom. Further, G is independently an epoxy group or a trialkoxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain an oxygen atom, or both. However, -(SiO)(H)R ³ -, - (SiO) (E) R ³ -, and - (SiO) (G) R ³ - bonding order is not limited).

In the above formula (2), b is an integer of 1 to 6, preferably an integer of 2 to 5, c is an integer of 1 to 4, preferably an integer of 1 to 3, and d is an integer of 1 to 4, Preferably, it is an integer of 1 to 3, and b+c+d is an integer of 4 to 10, preferably an integer of 4 to 8. However, the bonding order of -(SiO)(H)R ³ -, -(SiO)(E)R ³ -, and -(SiO)(G)R ³ - is not limited.

Further, R ³ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and examples thereof are the same as those exemplified as the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ¹ , R ⁶ , R ⁷ and R ⁸ .

Further, E is independently a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom, and is exemplified. The same group as the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group used for the above R ² . This E is a group which is appropriately introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

Further, G is an epoxy group and/or a trialkoxyalkylene group which are bonded to a ruthenium atom by a divalent hydrocarbon group which may contain an oxygen atom, independently of each other. Examples of such an epoxy group include those represented by the following formula (18).

In the above formula (18), an oxygen atom may be present in R ¹² , and it is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and specific examples thereof include a methylene group and a stretching group. An alkyl group such as a propyl group, a butyl group, a butyl group, a hexyl group or a octyl group; an alkylene group such as a cycloalkyl group, an oxyethyl group, an oxypropyl group or an oxybutyl group; Alkyl and the like.

Specific examples of such an epoxy group include the following.

On the other hand, the above trialkoxysulfanyl group is, for example, represented by the following formula (19).

In the above formula (19), R ¹³ is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and specific examples thereof include a methylene group, an exoethyl group, a stretching group, and a stretching group. a butyl group, a hexyl group, a cyclohexyl group, an extended alkyl group, and the like. In addition, R ¹⁴ is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and specific examples thereof include an alkyl group such as a methyl group, an ethyl group or an n-propyl group.

Specific examples of such a trialkoxyalkylene group include the following.

Examples of the component (D) include the following compounds.

【化39】

【化42】

【化44】

The component (D) may be used alone or in combination of two or more. In addition, the amount of the component (D) is in the range of 0.10 to 10.0 parts by mass, preferably 0.50 to 8.0 parts by mass, per 100 parts by mass of the component (A). When the amount is less than 0.10 parts by mass, sufficient adhesiveness cannot be obtained. When the amount is more than 10.0 parts by mass, the fluidity of the composition is deteriorated, and the physical strength of the cured product obtained by curing the composition of the present invention is lowered.

[(E) component]

The component (E) of the present invention is a carboxylic acid anhydride for improving the adhesion ability of the component (D) and promoting the self-adhesiveness of the cured product obtained by curing the composition of the present invention. As the component (E), any one which can be used as a curing agent for an epoxy resin can be used.

Such a component (E) is preferably the following formula (12) or the following A carboxylic anhydride represented by the formula (13).

(wherein q is an integer from 1 to 6, r is an integer from 1 to 4, s is an integer from 1 to 4, q+r+s is an integer from 4 to 10, and R ¹¹ is independently substituted or non-substituted. The substituted monovalent hydrocarbon group, which is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom. And Q is a cyclic carboxylic acid anhydride residue which is bonded to a ruthenium atom via a divalent hydrocarbon group independently of each other. However, -(SiO)(H)R ¹¹ -, -(SiO)(M)R ¹¹ - and - (SiO) (Q) R ¹¹ - The bonding sequence is not limited).

(wherein R ¹¹ , M, and Q are the same as described above, t is an integer of 1 to 3, u is an integer of 0 to 2, and t + u is 3).

In the above formula (12), q is an integer of 1 to 6, preferably an integer of 2 to 5, r is an integer of 1 to 4, preferably an integer of 1 to 3, and s is an integer of 1 to 4, Preferably, it is an integer of 1 to 3, and the sum of q, r and s is an integer of 4 to 10, preferably an integer of 4 to 8. However, the bonding order of -(SiO)(H)R ¹¹ -, -(SiO)(M)R ¹¹ - and -(SiO)(Q)R ¹¹ - is not limited.

Further, R ¹¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and examples thereof are the same as those of the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ¹ , R ³ , R ⁶ , R ⁷ and R ⁸ . base.

Further, M is independently a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to a ruthenium atom by a divalent hydrocarbon group which may contain a ruthenium atom, an oxygen atom or a nitrogen atom, and is exemplified by The above-mentioned R ² and E are the same groups as the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group. This M is a group which is suitably introduced from the viewpoint of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

In addition, the Q-based cyclic carboxylic anhydride residue which is bonded to the ruthenium atom by a divalent hydrocarbon group is specifically a group represented by the following formula (20).

In the above formula (20), R ^{15 is} preferably a divalent hydrocarbon group having 1 to 15 carbon atoms, and specific examples thereof include a methylene group, an exoethyl group, a propyl group, a butyl group, and the like. Base or propyl is excellent.

Examples of the component (E) represented by the above formula (12) include the following compounds.

【化49】

Next, in the above formula (13), t is an integer of 1 to 3, u is an integer of 0 to 2, t+u is 3, and R ¹¹ , M and Q are the same groups as described above.

Examples of the component (E) represented by the above formula (13) include the following compounds.

These (E) components may be used alone or in combination of two or more.

The blending amount of the component (E) is in the range of 0.010 to 10.0 parts by mass, preferably 0.10 to 5.0 parts by mass, per 100 parts by mass of the component (A). When it is less than 0.010 parts by mass, sufficient effects for promoting the adhesiveness of the composition of the present invention are not obtained, and when it exceeds 10.0 parts by mass, there will be The fluidity of the composition deteriorates and the preservation stability of the composition is impaired.

The curable composition for sealing an optical semiconductor of the present invention preferably contains the following component (F) as an optional component.

[(F) ingredient]

In the component (F) of the present invention, a cyclic organopolysiloxane represented by the following formula (3), which is a cured product obtained by curing the composition of the present invention, is preferably used to impart a better resistance. Impact person.

(wherein e is an integer from 1 to 4, f is an integer from 3 to 6, e+f is an integer from 4 to 10, and R ⁴ is independently substituted or unsubstituted monovalent hydrocarbon group, and J is independent of each other The ground is a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom, and the L system is independently bonded directly to each other. The alkenyl group of the ruthenium atom. However, the order of bonding of -(SiO)(J)R ⁴ - and -(SiO)(L)R ⁴ - is not limited).

In the above formula (3), e is an integer of 1 to 4, preferably an integer of 1 to 3, f is an integer of 3 to 6, preferably an integer of 3 to 5, and e+f is 4 to 10 An integer, preferably an integer from 4 to 8. However, the bonding order of -(SiO)(J)R ⁴ - and -(SiO)(L)R ⁴ - is not limited.

Further, examples of the R ⁴ -substituted or unsubstituted monovalent hydrocarbon group include the same examples as the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ¹ , R ³ , R ⁶ , R ⁷ , R ⁸ and R ¹¹ . .

Further, J is independently a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to a ruthenium atom by a divalent hydrocarbon group which may contain a ruthenium atom, an oxygen atom or a nitrogen atom, and is exemplified by The same group as the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group used for the above R ² , E, and M. This J is a group which is suitably introduced from the viewpoint of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

Further, L is directly bonded to an alkenyl group of a halogen atom, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and a nonenyl group. Among them, vinyl or allyl is particularly preferred.

Examples of such a component (F) include the following compounds.

【化54】

The component (F) may be used alone or in combination of two or more. In addition, the amount of the component (F) is preferably in the range of 0.10 to 50.0 parts by mass, more preferably 1.0 to 40.0 parts by mass, per 100 parts by mass of the component (A). When the amount is 0.10 parts by mass or more, the effect of imparting appropriate impact resistance to the cured product obtained by curing the composition of the present invention is sufficient, and when it is 50.0 parts by mass or less, the composition of the present invention is hardened and hardened. The crack resistance or low gas permeability of the hardened material.

[Other ingredients]

In the curable composition for sealing an optical semiconductor of the present invention, in order to improve In addition to the above components (A) to (E) and (F), a plasticizer, a viscosity modifier, a flexibility imparting agent, an inorganic filler, a reaction control agent, and (E) may be added as needed. Any of various admixtures such as a promoter other than the component. The blending amount of these additives is arbitrary.

As the plasticizer, the viscosity modifier, and the flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following formula (21) and/or a linear chain represented by the following formulas (22) and (23) may be used in combination. Polyfluoro compound. Rf-(T) _f' -CH=CH ₂ (21) wherein Rf is a group represented by the following formula (24), F-[CF(CF ₃ )CF ₂ O] _g' -C _{h '} F _2h' - (24) (wherein g' is preferably from 1 to 200, more preferably from 1 to 150, and h' is preferably an integer from 1 to 3). T is -CH ₂ -, -OCH ₂ -, -CH ₂ OCH ₂ - or -CO-NR ¹⁶ -X- (except that R ¹⁶ is a hydrogen atom, a methyl group, a phenyl group or an allyl group, and X is -CH) ₂ - a group represented by the following structural formula (25) or a group represented by the following structural formula (26).

f' is 0 or 1].

X'-O-(CF ₂ CF ₂ CF ₂ O) _i' -X' (22) (wherein X' is a base represented by C _j' F _2j'+1 - (j' is 1 to 3), i' is preferably an integer from 1 to 200, more preferably an integer from 2 to 100).

X'-O-(CF ₂ O) _k' (CF ₂ CF ₂ O) _l' -X' (23) (wherein X' is the same as above, and k' and l' are preferably 1~ An integer of 200, more preferably an integer of 1 to 100, and an average value of k'+l' is preferably 2 to 400, more preferably 2 to 300).

Specific examples of the polyfluoromonoalkenyl compound represented by the above formula (21) include the following. Further, in the following formula, Me represents a methyl group.

【化57】 (here, m'=1~100).

Specific examples of the linear polyfluoro compound represented by the above formulas (22) and (23) include the following.

CF ₃ O-(CF ₂ CF ₂ CF ₂ O) _n' -CF ₂ CF ₃

CF ₃ -[(OCF ₂ CF ₂ ) _o' (OCF ₂ ) _p' ]-O-CF ₃ (wherein n', o' and p' are preferably each an integer from 1 to 200, more preferably The integer of 1 to 150, the average value of o + p' is preferably an integer of 2 to 400, more preferably an integer of 2 to 300).

Further, the viscosity (23 ° C) of the polyfluoro compound represented by the above formulas (21) to (23) is the same as that of the component (A), and is 5.00 to 100,000 mPa. s, the special expectation is 50.0~50,000mPa. The range of s.

Examples of the inorganic fillers include cerium oxide powders such as aerosol-type cerium oxide, sedimentary cerium oxide, spherical cerium oxide, cerium oxide aerogel, or the like, or the surface of the cerium oxide powder is various organic a cerium oxide powder obtained by treating chlorosilane, an organic diazoxide or a cyclic organopolyazane; and further treating the surface of the cerium oxide powder with the monovalent perfluoro group represented by the above formula (14) a cerium oxide-based reinforcing filler such as an alkyl group or a cerium oxide powder obtained by reprocessing an organic decane or an organic decane having a monovalent perfluorooxyalkyl group represented by the above formula (15); Reinforcing or quasi-reinforcing fillers of fused silica powder, diatomaceous earth, calcium carbonate, etc.; inorganic pigments such as titanium oxide, iron oxide, carbon black, cobalt aluminate; titanium oxide, iron oxide, carbon black, cerium oxide, A heat-resistant enhancer such as barium hydroxide, zinc carbonate, magnesium carbonate or manganese carbonate; a heat conductivity imparting agent such as alumina, boron nitride, tantalum carbide or metal powder; and conductive materials such as carbon black, silver powder and conductive zinc Sexual imparting agent, etc. Further, inorganic fine particles having a refractive index of 1.50 or less at 25 ° C and 589 nm (D line of sodium) such as magnesium fluoride, aluminum fluoride, calcium fluoride, lithium fluoride, sodium fluoride, cesium fluoride or cerium oxide are used. Also useful as a reinforcing filler.

Examples of the control agent for the hydroquinone alkylation reaction catalyst include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, and 3,5-dimethyl-1. -hexyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylbutynol, etc. An acetylene alcohol; or a reactant of a chlorodecane having an identical monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group as the above G, and an ethynyl alcohol; 3-methyl-3-pentene-1-yne , 3,5-dimethyl-3-hexene-1-yne, triallyl isocyanurate, etc.; or polyvinyl siloxane, organophosphorus compound, etc., by this addition, moderately maintain the hardening reaction Sex and preservation stability.

Examples of the adhesion promoter other than the component (E) include an organic zirconium compound such as azirconium oxide or zirconium sulphate, or an organic titanium compound such as a titanium alkoxide or a titanium tong.

The method for producing the curable composition for sealing an optical semiconductor of the present invention is not particularly limited, and it can be produced by kneading the components (A) to (E) and (F) and other optional components. In this case, a mixing device such as a planetary mixer, a Ross mixer, a Hobart mixer, or the like, or a kneading device such as a kneader or a three-roller may be used as needed.

In the configuration of the curable composition for optical semiconductor sealing of the present invention, the so-called one liquid in which all of the above components (A) to (E), (F), and other optional components are used as one composition can be used depending on the application. The composition may be either a two-component type or a mixture of the two when used.

The curable composition for sealing an optical semiconductor of the present invention is cured by heating, and is provided with a cured product having good impact resistance, crack resistance, and low gas permeability. Therefore, it is useful as a protective LED, an IC, or the like. A sealing material such as an optical semiconductor element such as LSI or organic EL. The curing temperature of the curable composition for optical semiconductor sealing is not particularly limited, and is usually 20 to 250 ° C, preferably 40 to 200 ° C. Moreover, the curing time at this time can be appropriately selected for the crosslinking reaction and subsequent to various semiconductor packaging materials. The time at which the reaction is completed is generally preferably from 10 minutes to 10 hours, more preferably from 30 minutes to 8 hours.

The cured product obtained by curing the composition of the present invention has a hardness of a type A rubber hardness meter defined by JIS K6253-3:2012, and is 30 to 90, preferably 35 to 85. When it is less than 30, there is a problem that the impact resistance of the LED sealing material is not good. On the other hand, when it is higher than 90, there is a problem that the crack resistance of the LED sealing material is not good.

Further, the water vapor permeability of the cured product of 1 mm thick obtained by curing the composition of the present invention is preferably 15.0 g/m ² . Below day, more preferably 13.0 g/m ² . Below day. If it is 15.0g/m ² . When the cured product obtained by curing the composition of the present invention is used as a sealing material for LEDs in an optical semiconductor device in which silver is coated around the LED, the silver is not exposed to the sulfur-based gas. It is better to blacken and reduce the brightness. In addition, the water vapor transmission rate is a value measured by a water vapor permeability meter L80-5000 manufactured by Lyssy Co., Ltd. according to JIS K7129:2008.

Further, the viscosity of the composition of the present invention specified in JIS K7117-1:1999 at 23 ° C is preferably from 50.0 to 50,000 mPa from the viewpoint of handling workability. s, more preferably 100~30,000mPa. s. If it is 50.0mPa. Above s, the no-flowing property is too high, and it is difficult to control the filling of a certain amount of the dispenser in the LED package, so it is preferably 50,000 mPa. In the case of s or less, it is preferable that the composition is not filled in the LED package, and the leveling time is excessive, and the productivity is lowered.

Moreover, the cured product obtained by hardening the composition of the present invention is The refractive index at 25 ° C and 589 nm (the D line of sodium) is preferably 1.30 or more and less than 1.40. When the refractive index is in this range, the optical semiconductor device obtained by sealing the optical semiconductor element by curing the cured product of the present invention does not have the efficiency of taking out light emitted from the LED to the outside. It is preferable because the design of the optical semiconductor device is lowered.

Further, when the composition of the present invention is used, the composition can be dissolved in a suitable fluorine-based solvent at a desired concentration depending on the use and purpose, for example, 1,3-bis(trifluoromethyl)benzene, Fluorinert. (manufactured by 3M Company), perfluorobutyl methyl ether, perfluorobutyl ethyl ether or the like.

In this manner, when it is a curable composition for optical semiconductor sealing which contains the above-mentioned components (A) to (E), (F) and other optional components, and has the above characteristics, impact resistance and crack resistance can be obtained. A hardened material that is excellent and has low gas permeability.

The structure of the optical semiconductor device in which the curable composition for optical semiconductor sealing of the present invention can be used is not particularly limited. The optical semiconductor device of the present invention has an optical semiconductor element and a cured product obtained by curing the above-described optical semiconductor sealing curable composition of the present invention for sealing the optical semiconductor element. The representative cross-sectional structure is shown in FIG. And Figure 2.

In the optical semiconductor device (light-emitting device) 10 of FIG. 1, the end portion 2a of the first lead frame 2 is provided with a mortar-shaped concave portion 2' whose opening diameter is gradually increased from the bottom surface thereof, and the concave portion 2' is formed in the concave portion 2 On the bottom surface, the LED chip 1 is passed through a silver paste or the like and bonded and fixed by a die bond, whereby the first lead frame 2 and an electrode (not shown) on one side of the bottom surface of the LED chip 1 are electrically connected. connection. Furthermore, the bottom surface of the recess 2' is silver. Further, the front end portion 3a of the second lead frame 3 and the other electrode (not shown) on the upper side surface of the LED chip 1 are electrically connected to each other through the bonding wires 4.

Further, in the recessed portion 2', the LED wafer 1 is covered with a sealing material 5 composed of a cured product obtained by curing the curable composition for optical semiconductor sealing of the present invention.

Further, the LED chip 1, the upper end portion 2a of the first lead frame 2, the upper end of the terminal portion 2b, the front end portion 3a of the second lead frame 3, and the upper end of the terminal portion 3b are translucent with the convex lens portion 6 at the tip end. The resin portion 7 is covered/sealed. Further, the lower end of the terminal portion 2b of the first lead frame 2 and the lower end of the terminal portion 3b of the second lead frame 3 penetrate the lower end portion of the translucent resin portion 7 and protrude outward.

In the optical semiconductor device (light-emitting device) 10' of FIG. 2, a mortar-shaped recessed portion 8' whose opening diameter is gradually increased from the bottom surface is provided on the upper surface of the package substrate 8, and is placed on the bottom surface of the recessed portion 8'. The LED wafer 1 is then fixed by a die bond, and the electrodes of the LED chip 1 are electrically connected to the electrodes 9 provided on the package substrate 8 by bonding wires 4. Further, the bottom surface of the concave portion 8' is plated with silver.

Further, in the recessed portion 8', the LED wafer 1 is covered with a sealing material 5 composed of a cured product obtained by curing the curable composition for optical semiconductor sealing of the present invention.

Here, the LED chip 1 is not particularly limited, and a light-emitting element used in a conventionally known LED chip can be used. As such a light-emitting element, for example, by MOCVD method, HDVPE Various methods such as a method and a liquid phase growth method are required to laminate a semiconductor material on a substrate provided with a buffer layer of GaN or AlN. As the substrate at this time, various materials can be used, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Among these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and industrial use value is high.

Examples of the semiconductor material to be laminated include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN, SiC, and the like. Among these, from the viewpoint of obtaining high luminance, a nitride-based compound semiconductor (In _x Ga _y Al _z N) is preferable. Such materials may also contain an activator or the like.

Examples of the structure of the light-emitting element include homojunction with MIS bonding, pn bonding, and PIN bonding; heterojunction or double heterostructure. Also, it can be a single or multiple quantum well structure.

A passivation layer may or may not be provided in the light-emitting element.

The light-emitting wavelength of the light-emitting element can be used from the ultraviolet region to the infrared region. However, when the main emission peak wavelength is 550 nm or less, the effect of the present invention is particularly remarkable.

The light-emitting element to be used can emit light in a single color in one type, or can emit light in a single color or a plurality of colors using a plurality of types.

The electrode can be formed on the light-emitting element by a conventionally known method.

The electrode on the light-emitting element can be connected to the lead end in various ways The child is electrically connected. The electrical connection member preferably has good ohmic mechanical connectivity with the electrode of the light-emitting element, and examples thereof include gold, silver, copper, platinum, aluminum, or the like, as described in FIGS. 1 and 2 . Bonding leads 4. Further, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Among these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

Further, the first lead frame 2 and the second lead frame 3 are made of copper, a copper-zinc alloy, an iron-nickel alloy or the like.

Further, the material for forming the light-transmitting resin portion 7 is not particularly limited as long as it is a material having light transmissivity, and an epoxy resin or a polyoxymethylene resin is mainly used.

Further, the package substrate 8 can be produced using various materials, and examples thereof include polyphthalic acid phthalamide (PPA), polycarbonate resin, polyphenylene sulfide resin, polybutylene terephthalate resin, and polyamine. Resin, liquid crystal polymer, epoxy resin, acrylic resin, polyoxynoxy resin, modified polyoxynoxy resin, ABS resin, BT resin, ceramics, and the like. Among these, polybutylphthalate (PPA) is particularly preferred from the viewpoint of heat resistance, strength, and cost. Further, it is preferable to mix a white pigment such as barium titanate, titanium oxide, zinc oxide or barium sulfate on the package substrate 8 to improve the reflectance of light.

Then, the sealing material 5 of the LED wafer 1 is coated so that the light from the LED chip 1 is efficiently penetrated to the outside, and the LED chip 1 or the bonding leads 4 are protected from external force, dust, or the like. As the sealing material 5, a cured product of the composition of the present invention is used. The sealing material 5 may also contain a fluorescent substance, a light diffusing member, or the like.

As described above, the curable composition for sealing an optical semiconductor of the present invention has excellent impact resistance, and therefore the optical semiconductor device 10, 10' of the present invention for sealing the optical semiconductor element using the composition can be It is manufactured without damaging its components.

The curable composition for optical semiconductor sealing of the present invention is excellent in impact resistance and crack resistance, and has a low gas permeability and a cured product. Therefore, the optical semiconductor obtained by sealing the optical semiconductor element with the cured product is obtained. When the device is arranged in a certain direction/posture using the bowl-shaped vibrating part feeder in the manufacturing step, for example, even if the optical semiconductor devices collide with each other, damage to members such as disconnected wires of the bonding wires is less likely to occur, so that the yield can be improved. And productive. Further, even if the temperature cycle test is performed, cracks are less likely to occur in the cured product, so that reliability can be improved. Further, even if it is used in an environment exposed to a sulfur-based gas, the sulfur-based gas does not easily penetrate the cured product, so that the decrease in brightness can be suppressed.

Moreover, the curable composition for optical semiconductor sealing of the present invention can be suitably used as a sealing material for protecting an LED from the above-described characteristics of the cured product.

[Examples]

Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited by the following examples. In addition, the viscosity is a measured value specified by JIS K7117-1:1999 at 23 °C.

(Example 1)

To 100 parts by mass of a linear polyfluoro compound (viscosity 10,900 mPa·s, vinyl group amount: 0.0123 mol/100 g) represented by the following formula (27), platinum-divinyltetramethyldifluorene is sequentially added. 0.15 parts by mass of a toluene solution of alkane complex (platinum concentration: 0.5% by mass), 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, and organic hydrogen polymerization represented by the following formula (28) 11.3 parts by mass of a siloxane (the amount of the SiH group is 0.00109 mol/g), 2.0 parts by mass of the cyclic organopolyoxane represented by the following formula (29), and 0.50 by mass of the carboxylic anhydride represented by the following formula (30). Mix and mix until uniform. Thereafter, the composition was prepared by performing a defoaming operation.

【化59】

(Example 2)

To 100 parts by mass of a linear polyfluoro compound (viscosity 4,010 mPa·s, vinyl group 0.0299 mol/100 g) represented by the following formula (31), platinum-divinyltetramethyl dioxane is sequentially added. 0.15 parts by mass of a toluene solution of alkane complex (platinum concentration: 0.5% by mass), 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, and a fluorine-containing organic compound represented by the following formula (32) Hydrogen polyoxyalkylene (SiH group amount: 0.0090 mol/g) 15.7 parts by mass, 2.5 parts by mass of a cyclic organopolyoxane represented by the following formula (33), and a carboxylic anhydride represented by the following formula (34) 0.30 parts by mass, mixed until homogeneous. Thereafter, the composition was prepared by performing a defoaming operation.

【化60】

(Example 3)

To 100 parts by mass of a linear polyfluoro compound (viscosity: 4,150 mPa·s, a vinyl group of 0.0603 mol/100 g) represented by the following formula (35), platinum-divinyltetramethyldioxane is sequentially added. 0.15 parts by mass of a toluene solution of alkane complex (platinum concentration: 0.5% by mass), 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, and organic hydrogen polymerization represented by the following formula (36) 31.2 parts by mass of a siloxane (the amount of the SiH group is 0.00193 mol/g), 3.0 parts by mass of the cyclic organopolyoxane represented by the following formula (37), and a carboxylic acid anhydride of 0.40 by the following formula (38). Mix and mix until uniform. Thereafter, the composition was prepared by performing a defoaming operation.

【化63】

(Example 4)

To 100 parts by mass of a linear polyfluoro compound (viscosity of 4,310 mPa·s, a vinyl group of 0.0909 mol/100 g) represented by the following formula (39), platinum-divinyltetramethyl dioxane is sequentially added. 0.15 parts by mass of a toluene solution of alkane complex (platinum concentration: 0.5% by mass), 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, and organic hydrogen polymerization represented by the following formula (40) 46.4 parts by mass of a siloxane (the amount of SiH is 0.00196 mol/g), 3.0 parts by mass of the cyclic organopolyoxane represented by the following formula (41), and 0.30 mass of the carboxylic anhydride represented by the following formula (42). Mix and mix until uniform. After that, by performing a defoaming operation To formulate the composition.

(Example 5)

To 50.0 parts by mass of the linear polyfluoro compound represented by the above formula (31), 0.15 parts by mass of a toluene solution (platinum concentration: 0.5% by mass) of platinum-divinyltetramethyldioxane complex was sequentially added, 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, 50.0 parts by mass of a linear polyfluoro compound represented by the above formula (35), and an organic hydrogen group represented by the following formula (45) 30.1 parts by mass of a siloxane (the amount of the SiH group is 0.0150 mol/g), 3.0 parts by mass of the cyclic organopolyoxane represented by the above formula (41), and 0.30 parts by mass of the carboxylic anhydride represented by the above formula (42). Mix until it becomes homogeneous. Thereafter, the composition was prepared by performing a defoaming operation.

(Example 6)

To 25.0 parts by mass of the linear polyfluoro compound represented by the above formula (31), a toluene solution (platinum concentration: 0.5% by mass) of platinum-divinyltetramethyldioxane complex was added in order of 0.15 parts by mass. 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, 75.0 parts by mass of a linear polyfluoro compound represented by the above formula (39), and an organic hydrogen group represented by the above formula (32) 39.8 parts by mass of a siloxane, 3.0 parts by mass of a cyclic organopolyoxane represented by the above formula (41), and 0.30 parts by mass of a carboxylic anhydride represented by the above formula (42), mixed To become even. Thereafter, the composition was prepared by performing a defoaming operation.

(Example 7)

To 100 parts by mass of the linear polyfluoro compound represented by the above formula (31), a toluene solution (platinum concentration: 0.5% by mass) of 0.20 parts by mass of platinum-divinyltetramethyldioxane complex is sequentially added. 0.25 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, 53.3 parts by mass of an organic hydrogen polyoxyalkylene represented by the above formula (32), and a cyclic organic compound represented by the above formula (33) 3.5 parts by mass of polysiloxane, 0.50 parts by mass of the carboxylic acid anhydride represented by the above formula (34), and a cyclic organopolyoxane (vinyl group amount: 0.357 mol/100 g) 20.0 mass represented by the following formula (43) Mix and mix until uniform. Thereafter, the composition was prepared by performing a defoaming operation.

(Example 8)

To 100 parts by mass of the linear polyfluoro compound represented by the above formula (35), platinum-divinyltetramethyldioxane complex toluene is sequentially added. 0.20 parts by mass of a solution (platinum concentration: 0.5% by mass), 0.25 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, and 89.7 parts by mass of an organohydrogenpolyoxyalkylene represented by the above formula (36). 3.5 parts by mass of the cyclic organopolyoxane represented by the above formula (37), 0.60 parts by mass of the carboxylic anhydride represented by the above formula (38), and a cyclic organopolyoxane represented by the following formula (44) ( The amount of vinyl group was 0.451 mol/100 g) 25.0 parts by mass, and it was mixed until it became uniform. Thereafter, the composition was prepared by performing a defoaming operation.

(Example 9)

To 100 parts by mass of the linear polyfluoro compound represented by the above formula (39), a toluene solution (platinum concentration: 0.5% by mass) of 0.25 parts by mass of platinum-divinyltetramethyldioxane complex is sequentially added. 0.30 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, 115 parts by mass of an organohydrogenpolyoxyalkylene represented by the above formula (40), and a cyclic organic compound represented by the above formula (41) 4.0 parts by mass of polysiloxane, 0.60 parts by mass of the carboxylic acid anhydride represented by the above formula (42), and 30.0 parts by mass of the cyclic organopolyoxane represented by the above formula (44) were mixed until uniform. Thereafter, the composition was prepared by performing a defoaming operation.

(Embodiment 10)

To 25.0 parts by mass of the linear polyfluoro compound represented by the above formula (31), a toluene solution (platinum concentration: 0.5% by mass) of 0.25 parts by mass of platinum-divinyltetramethyldioxane complex was sequentially added. 0.30 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, 75.0 parts by mass of a linear polyfluoro compound represented by the above formula (39), and an organic hydrogen group represented by the above formula (32) 111 parts by mass of the oxirane, 4.0 parts by mass of the cyclic organopolyoxane represented by the above formula (41), 0.60 parts by mass of the carboxylic anhydride represented by the above formula (34), and a ring represented by the above formula (44) 30.0 parts by mass of the organic polyoxyalkylene was mixed until it became homogeneous. Thereafter, the composition was prepared by performing a defoaming operation.

(Comparative Example 1)

In addition to the above-described Example 2, the amount of the organohydrogenpolyoxane shown in the above formula (32) was changed to 128 parts by mass, and the cyclic organopolyoxane 60.0 represented by the above formula (43) was added. A composition was prepared in the same manner as in Example 2 except for the mass portion.

(Comparative Example 2)

In addition to the above Example 2, the organohydrogen polyoxyalkylene represented by the above formula (32) was changed to an organohydrogenpolyoxyalkylene represented by the following formula (46) (the amount of SiH was 0.00499 mol/g). A composition was prepared in the same manner as in Example 2 except for 5.99 parts by mass.

【化69】

(Comparative Example 3)

In addition to the above Example 2, the organohydrogen polyoxyalkylene represented by the above formula (32) was changed to an organohydrogenpolyoxyalkylene represented by the following formula (47) (the amount of SiH was 0.00210 mol/g). A composition was prepared in the same manner as in Example 2 except for 14.2 parts by mass.

(Comparative Example 4)

In addition to the above embodiment 2, the organic hydrogen represented by the above formula (32) The polyoxyalkylene is changed to 24.1 parts by mass of the organohydrogen polyoxyalkylene represented by the above formula (46), and 20.0 parts by mass of the cyclic organopolyoxane represented by the above formula (44) is added, and examples and examples are given. 2 The composition was prepared in the same manner.

(Comparative Example 5)

In addition to the above Example 2, the organic hydrogen polyoxyalkylene represented by the above formula (32) was changed to 57.2 parts by mass of the organohydrogen polyoxyalkylene represented by the above formula (47), and the above formula (44) was added. A composition was prepared in the same manner as in Example 2 except that 20.0 parts by mass of the cyclic organopolyoxane shown was used.

The following items were evaluated for each composition. Further, the curing conditions were 150 ° C × 5 hours. The results are summarized in Tables 1 and 2.

1. Viscosity of composition: Measured at 23 ° C according to JIS K7117-1:1999.

2. Hardness: A sheet-like cured product having a thickness of 2 mm was produced and measured in accordance with JIS K6253-3:2012.

3. Refractive index: A sheet-like cured product having a thickness of 2 mm was produced, and the refractive index at 25 ° C and 589 nm (D line of sodium) was measured using a multi-wavelength Abbe refractometer DR-M2/1550 (manufactured by Atago Co., Ltd.).

4. Water Vapor Transmission Rate: A sheet-like cured product having a thickness of 1 mm was prepared and measured using a water vapor permeability meter of L80-5000 manufactured by Lyssy Co., Ltd. according to JIS K7129:2008. Further, the measurement temperature was 40 ° C, and the area of the cured product used for the measurement was 50 cm ² .

5. Impact resistance of the cured product: In the optical semiconductor device having the same configuration as that of the embodiment of Fig. 2, in order to form the sealing material 5, the above-mentioned The obtained composition was poured into the concave portion 8' so as to be immersed in the recessed portion 8', and heated at 150 ° C for 5 hours to prepare an optical semiconductor device in which the LED wafer 1 was sealed with a cured product of the composition. Then, 1,000 of the optical semiconductor devices were placed in a bowl-shaped vibrating part feeder and arranged, and the number of broken leads of the bonding leads was counted.

6. Crack resistance of cured product: 10 optical semiconductor devices fabricated in the same manner as described above were placed at -40 ° C for 10 minutes, and then placed at 100 ° C for 10 minutes, which was repeated for 1 cycle. 500 cycles were used for the temperature cycle test. After the test, the appearance of the cured product was visually observed, and the number of crack occurrences was counted.

7. Gas permeability of the cured product: The optical semiconductor device fabricated in the same manner as described above was placed in a hydrogen sulfide gas atmosphere at 10 ° C for 10 hours at 100 ° C, and visually confirmed by silver on the bottom surface of the concave portion 8'. The degree of discoloration.

As a result of the results of Tables 1 and 2, it is understood that the cured product obtained by curing the curable composition for optical semiconductor sealing of the present invention (Examples 1 to 10) has good impact resistance as compared with Comparative Examples 1 to 5. , crack resistance and low gas permeability, so no breakage or cracking of the bonding wire was observed, and no discoloration of silver was observed.

From the above results, it is apparent that when the curable composition for optical semiconductor sealing of the present invention is used, a cured product having excellent impact resistance and crack resistance and having low gas permeability can be obtained, and such an optical semiconductor is exhibited. The curable composition for sealing is suitable as a sealing material for an optical semiconductor element.

Furthermore, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and have substantially the same configuration as the technical idea described in the patent application scope of the present invention, and the same effects are exhibited, and any of them are included in the technical scope of the present invention.

1‧‧‧LED chip

2‧‧‧First lead frame

2a‧‧‧The front end of the first lead frame

2b‧‧‧ Terminal part of the first lead frame

2'‧‧‧ recess

3‧‧‧Second lead frame

3a‧‧‧ front end of the second lead frame

3b‧‧‧ Terminal part of the second lead frame

4‧‧‧ Bonding leads

5‧‧‧ Sealing material

6‧‧‧ convex lens

7‧‧‧Transparent resin department

10‧‧‧Optical semiconductor devices

Claims (15)

A curable composition for sealing a photo-semiconductor comprising (A) one molecule having two or more alkenyl groups, further having a perfluoropolyether structure in the main chain, and an alkenyl group content of 0.0050 to 0.200 mol/100 g The linear polyfluorinated compound: 100 parts by mass, (B) an organohydrogen polyoxyalkylene represented by the following formula (1), (wherein, a is an integer of from 3 to 10, and A is a divalent organic group containing a perfluoroalkylene group, a perfluoroalkylalkylene group, or both thereof, and D is independently of each other and may contain a halogen atom, oxygen a substituted or unsubstituted divalent hydrocarbon group of an atom or a nitrogen atom, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and R ² is independently a hydrogen atom or may contain a halogen atom or an oxygen atom. Or a monovalent perfluoroalkyl group bonded to a ruthenium atom or a monovalent perfluoroalkyl group bonded to a ruthenium atom, and three or more of R ² are a hydrogen atom; (C) a platinum group metal contact Medium: 0.1 to 500 ppm in terms of a platinum group metal atom, (D) a cyclic organopolyoxane represented by the following formula (2): 0.10 to 10.0 parts by mass, [Chemical 2] (wherein b is an integer from 1 to 6, c is an integer from 1 to 4, d is an integer from 1 to 4, b+c+d is an integer from 4 to 10, and R ³ is independently substituted or not The substituted monovalent hydrocarbon group, which is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom. Further, G is an epoxy group or a trialkoxyalkyl group bonded to a halogen atom independently of each other via a divalent hydrocarbon group which may contain an oxygen atom, or both, but -(SiO)(H)R ³ -, - (SiO) (E) R ³ -, and - (SiO) (G) R ³ - bonding order is not limited); (E) carboxylic anhydride: 0.010 ~ 10.0 parts by mass of optical semiconductor sealing hardening And a blending amount of the component (B), which is directly bonded to the ruthenium atom in the component (B), relative to the alkenyl group 1 mole contained in the composition. The hardness of the cured product obtained by curing the curable composition for sealing an optical semiconductor seal is 0.50 to 2.0 mol, and the hardness of the A-type rubber according to JIS K6253-3:2012 is 30 to 90. The value of the person. The curable composition for sealing an optical semiconductor according to claim 1, which further comprises 0.10 to 50.0 parts by mass of the cyclic organopolyoxane represented by the following formula (3) as a component (F). (wherein e is an integer from 1 to 4, f is an integer from 3 to 6, e+f is an integer from 4 to 10, and R ⁴ is independently substituted or unsubstituted monovalent hydrocarbon group, and J is independent of each other The ground is a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom, and the L system is independently bonded directly to each other. In the alkenyl group of the ruthenium atom, the order of bonding of -(SiO)(J)R ⁴ - and -(SiO)(L)R ⁴ - is not limited). The curable composition for sealing an optical semiconductor according to claim 1, wherein the component (A) is a linear polyfluoro compound represented by the following formula (4). (wherein R ⁶ and R ⁷ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and one or more of them are alkenyl groups. R ⁸ is independently a hydrogen atom, or a substituted or unsubstituted one. The monovalent hydrocarbon group, g and h are each an integer from 1 to 150, and the average value of g+h is 2 to 300, and i is an integer of 0 to 6). The curable composition for sealing an optical semiconductor according to claim 1, wherein the component (A) is selected from the group consisting of the following general formula (5), the following general formula (6), and the following general formula (7); One or more linear polyfluoro compounds in the group, (wherein R ⁸ is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and g and h are each an integer of from 1 to 150, and an average value of g + h is from 2 to 300, i is An integer of 0 to 6, wherein R ⁹ is independently a substituted or unsubstituted monovalent hydrocarbon group; (wherein R ⁸ , R ⁹ , g, h, and i are the same as described above); (wherein R ⁸ , g, h, and i are the same as described above). The curable composition for sealing an optical semiconductor according to claim 1, wherein the perfluoroalkylalkylene group contained in the component (B) contains 1 to 500 repeats represented by the following formula (8). The basis of the unit, -C _e' F _2e' O- (8) (wherein e' is an integer of 1 to 6 per unit independently). The curable composition for sealing an optical semiconductor according to claim 1, wherein the component (B) is selected from the group consisting of the following general formula (9), the following general formula (10), and the following general formula (11). ) the basis of the group, (wherein R ¹⁰ is independently a fluorine atom or a CF ₃ group, j is an integer of 1 to 4, and k and n are each an integer of 0 to 200, and an average value of k + n is 0 to 400, and l is An integer from 2 to 6, in addition, the order of bonding of each repeating unit is not limited); (where p is an integer from 1 to 200, and j is the same as above); (In the formula, R ¹⁰ , j, k, and n are the same as described above, and the order of bonding of each repeating unit is not limited). The curable composition for sealing an optical semiconductor according to claim 1, wherein the component (E) is selected from the group consisting of carboxylic anhydrides of the following formula (12) and the following formula (13); 】 (wherein q is an integer from 1 to 6, r is an integer from 1 to 4, s is an integer from 1 to 4, q+r+s is an integer from 4 to 10, and R ¹¹ is independently substituted or not The substituted monovalent hydrocarbon group, which is independently a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a ruthenium atom via a divalent hydrocarbon group which may contain a halogen atom, an oxygen atom or a nitrogen atom. , Q is independently a cyclic carboxylic anhydride residue bonded to a ruthenium atom via a divalent hydrocarbon group, but -(SiO)(H)R ¹¹ -, -(SiO)(M)R ¹¹ - and - (SiO) (Q) R ¹¹ - bonding order is not limited); (wherein R ¹¹ , M, and Q are the same as described above, t is an integer of 1 to 3, u is an integer of 0 to 2, and t + u is 3). The curable composition for sealing an optical semiconductor according to claim 1, wherein the monovalent perfluoroalkyl group or the monovalent group contained in R ^{2 in the} above formula (1) and E in the above formula (2) The fluorooxyalkyl group is a group represented by the following formula (14) or formula (15) independently of each other, and C _v F _2v+1 - (14) (wherein v is an integer of 1 to 10) ; (where w is an integer from 1 to 10). The curable composition for sealing an optical semiconductor according to claim 2, wherein the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group contained in J in the above formula (3) is independently of each other a group represented by the following formula (14) or formula (15), C _v F _2v+1 - (14) (wherein v is an integer of 1 to 10); (where w is an integer from 1 to 10). The curable composition for sealing an optical semiconductor according to claim 7, wherein the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group contained in M in the above formula (12) is independently of each other a group represented by the following formula (14) or formula (15), C _v F _2v+1 - (14) (wherein v is an integer of 1 to 10); (where w is an integer from 1 to 10). The curable composition for sealing an optical semiconductor according to claim 1, wherein the cured product having a thickness of 1 mm obtained by curing the curable composition for optical semiconductor sealing has a water vapor transmission rate of 15.0 g/m ² . Below day. The curable composition for sealing an optical semiconductor according to claim 1, wherein the curable composition for optical semiconductor sealing has a viscosity at 23 ° C as defined in JIS K7117-1:1999, and is 50.0 to 50,000 mPa. s. The curable composition for sealing an optical semiconductor according to any one of Claims 1 to 12, wherein the cured product obtained by curing the curable composition for optical semiconductor sealing is cured at 25 ° C and 589 nm (D line of sodium) The refractive index is 1.30 or more and less than 1.40. An optical semiconductor device characterized by having an optical semiconductor element and a cured product obtained by curing the curable composition for sealing an optical semiconductor according to any one of claims 1 to 13 in order to seal the optical semiconductor element . The optical semiconductor device of claim 14, wherein the optical semiconductor component is a light emitting diode.