JP6546004B2 - Curable composition for encapsulating an optical semiconductor and optical semiconductor device using the same - Google Patents

Description

  The present invention relates to a curable composition for encapsulating 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, directly linked to a silicon atom in one molecule From a composition comprising a fluorine-containing organohydrogenpolysiloxane having two or more hydrogen atoms and a platinum group compound, properties such as heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, low temperature properties, etc. It has been proposed to obtain an excellent cured product with a well-balanced ratio (Patent Document 1).

  Then, a composition is proposed in which self-adhesiveness is imparted to a metal or a plastic substrate by adding an organopolysiloxane having a hydrosilyl group and an epoxy group and / or a trialkoxysilyl group to the composition described above. (Patent Document 2).

  Furthermore, a composition is proposed in which the adhesion to various substrates, in particular polyphenylene sulfide resin (PPS) and polyamide resin, is improved by adding a carboxylic acid anhydride to the above-mentioned composition (Patent Document 3) ).

  And it is proposed that a photosemiconductor element, especially a light emitting diode (henceforth "LED") is sealed with a hardened material obtained by hardening these compositions (patent documents 4-7).

  By the way, in recent years, with the increase in luminance of LEDs, the amount of heat generation from the LEDs at the time of lighting has been increasing. Therefore, due to the heat, a cured product obtained by curing the above composition turns yellow over time, often causing a problem that the brightness of the LED decreases. For example, in the case of an LED that emits light at a wavelength of 450 nm, when the cured product turns yellow, the transmittance of the cured product to the light decreases, and the brightness of the LED decreases.

  In addition, in the case of an optical semiconductor device in which an LED is sealed, the periphery of the LED may be plated with silver or the like to increase the brightness. When the optical semiconductor device in which the LED is sealed with a cured product obtained by curing the composition described above is used in an environment exposed to a sulfur-based gas, the sulfur-based gas permeates the cured product with time and silver In order to change the color to black, there was a problem that the brightness decreased. From the above, it has been desired that such a composition has a small color change due to heat and a low gas permeability as a cured product obtained by curing.

Patent No. 2990646 gazette Patent No. 3239717 Patent No. 3567973 gazette Patent No. 5653877 gazette JP, 2014-005328, A JP, 2014-012810, A JP, 2014-091778, A

  The present invention has been made in view of the above problems, and it is a curable composition for encapsulating an optical semiconductor which gives a cured product having good heat resistance and low gas permeability, and the optical semiconductor for encapsulating the same. An object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is sealed by a cured product obtained by curing the curable composition.

（式中、ａは１〜５０の整数であり、ｂは１〜５０の整数であり、ａ＋ｂは２〜１００の整数であり、Ａは、互いに独立して、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｒ^１は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｒ^２は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｒ^３は互いに独立して置換又は非置換の１価の炭化水素基である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^２−及び−（ＳｉＯ）（Ａ）Ｒ^３−の結合の順番は限定されない。）
（Ｃ）白金族金属系触媒：白金族金属原子換算で０．１〜５００ｐｐｍ、
（Ｄ）一分子中にケイ素原子に直結した水素原子と、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基と、酸素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合したエポキシ基若しくはトリアルコキシシリル基又はその両方とを有するオルガノポリシロキサン：０．１０〜１０．０質量部、
（Ｅ）下記一般式（２）で表される、一分子中にケイ素原子に直結した１価の不飽和炭化水素基と、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基とを有する環状オルガノポリシロキサン：０．５０〜３０．０質量部

（式中、ｃは１〜４の整数、ｄは３〜６の整数、ｃ＋ｄは４〜１０の整数、Ｒ^４は置換又は非置換の１価の炭化水素基、Ｄは酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基、Ｅはケイ素原子に直結した１価の不飽和炭化水素基である。ただし、−（ＳｉＯ）（Ｄ）Ｒ^４−及び−（ＳｉＯ）（Ｅ）Ｒ^４−の結合の順番は限定されない。）
を含有する光半導体封止用硬化性組成物であって、前記（Ｂ）成分の配合量は、前記（Ａ）成分のアルケニル基と前記（Ｅ）成分の１価の不飽和炭化水素基の合計１モルに対して、前記（Ｂ）成分に含まれるケイ素原子に直結した水素原子が０．５０〜２．０モルとなる量であり、前記光半導体封止用硬化性組成物を硬化して得られる２ｍｍ厚の硬化物を１５０℃下１，０００時間放置した後の、４５０ｎｍの波長の光に対する透過率が初期の９０．０％以上であり、前記光半導体封止用硬化性組成物を硬化して得られる１ｍｍ厚の硬化物の水蒸気透過率が、２０．０ｇ／ｍ^２・ｄａｙ以下であることを特徴とする光半導体封止用硬化性組成物を提供する。 In order to achieve the above object, the present invention (A) has two or more alkenyl groups in one molecule, further has a perfluoropolyether structure in the main chain, and has an alkenyl group content of 0. 100 parts by mass of a linear polyfluoro compound having a molecular weight of from .0050 to 0.200 mol / 100 g,
(B) an organohydrogenpolysiloxane represented by the following general formula (1):

(Wherein, a is an integer of 1 to 50, b is an integer of 1 to 50, a + b is an integer of 2 to 100, and A is independently of each other a silicon atom, an oxygen atom or a nitrogen atom And a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain one or more of R ^{1 s} independently of ^one another is substituted or unsubstituted 1 And R ² is independently of each other a substituted or unsubstituted monovalent hydrocarbon group, and R ³ is independently of each other a substituted or unsubstituted monovalent hydrocarbon group. However, the order of bonding of-(SiO) (H) R ^2- and-(SiO) (A) R ^3- is not limited.)
(C) Platinum group metal based catalyst: 0.1 to 500 ppm in terms of platinum group metal atom,
(D) A monovalent perfluoroalkyl group bonded to a silicon atom via a hydrogen atom directly bonded to a silicon atom in one molecule, and a silicon atom, an oxygen atom or a divalent hydrocarbon group which may contain a nitrogen atom or Organopolysiloxanes having a monovalent perfluorooxyalkyl group and an epoxy group or trialkoxysilyl group or both bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom: 0.10 ~ 10.0 parts by mass,
(E) A monovalent unsaturated hydrocarbon group directly linked to a silicon atom, represented by the following general formula (2), and a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom Cyclic organopolysiloxane having a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom: 0.50 to 30.0 parts by mass

(Wherein, c is an integer of 1 to 4; d is an integer of 3 to 6; c + d is an integer of 4 to 10; R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group; D is an oxygen atom or a nitrogen atom Or a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain at least one substituent, and E is a monovalent unsaturated hydrocarbon group directly bonded to a silicon atom However, the order of bonding of-(SiO) (D) R ^4- and-(SiO) (E) R ^4- is not limited.)
The curable composition for optical semiconductor encapsulation according to claim 1, wherein the compounding amount of the component (B) is the alkenyl group of the component (A) and the monovalent unsaturated hydrocarbon group of the component (E). The amount of hydrogen atoms directly bonded to the silicon atoms contained in the component (B) is 0.50 to 2.0 moles relative to 1 mole in total, and the curable composition for encapsulating an optical semiconductor is cured. Transmittance of the light having a wavelength of 450 nm after leaving the obtained 2 mm thick cured product at 150 ° C. for 1,000 hours is 90.0% or more of the initial thickness, and the curable composition for encapsulating an optical semiconductor as described above And a water vapor transmission rate of a cured product of 1 mm thickness obtained by curing the cured product is 20.0 g / m ² · day or less.

  As described above, when all of the components (A) to (E) are contained, and the cured product is left at 150 ° C. for 1,000 hours, the transmittance for light of a wavelength of 450 nm is 90.0% or more of the initial value. If it is a curable composition for optical semiconductor sealing which is an addition-curable fluoropolyether-based curable composition having a water vapor transmission rate in the above range, a cured product having good heat-resistant discoloration and low gas permeability You can get Therefore, the cured product of the curable composition for encapsulating an optical semiconductor can be suitably used as an encapsulant for an optical semiconductor element, particularly, an encapsulant for protecting an LED.

Furthermore, it is preferable to contain carboxylic anhydride: 0.010-5.0 mass parts as (F) component.

  As described above, when all of the components (A) to (F) are contained and the cured product is left at 150 ° C. for 1,000 hours, the transmittance for light of a wavelength of 450 nm is 90.0% or more of the initial value If it is a curable composition for encapsulating an optical semiconductor, which is an addition-curable fluoropolyether-based curable composition having a water vapor transmission rate in the above range, it has good heat discoloration resistance and low gas permeability, A cured product having even better adhesion can be obtained.

（式中、Ｒ^５及びＲ^６は互いに独立して、アルケニル基、又は、置換若しくは非置換の１価の炭化水素基であり、二つ以上はアルケニル基である。Ｒ^７は互いに独立して、水素原子、又は、置換若しくは非置換の１価の炭化水素基であり、ｅ及びｆはそれぞれ１〜１５０の整数であって、且つｅ＋ｆの平均値は２〜３００であり、ｇは０〜６の整数である。） Moreover, it is preferable that the said (A) component is a linear polyfluoro compound represented by following General formula (3).

(Wherein R ⁵ and R ⁶ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and two or more are an alkenyl group. R ⁷ is independently of each other A hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, e and f each represents an integer of 1 to 150, and the average value of e + f is 2 to 300, and g is 0 to It is an integer of 6.)

（式中、Ｒ^７は互いに独立して、水素原子、又は、置換若しくは非置換の１価の炭化水素基であり、ｅ及びｆはそれぞれ１〜１５０の整数であって、且つｅ＋ｆの平均値は２〜３００であり、ｇは０〜６の整数であり、Ｒ^８は互いに独立して置換又は非置換の１価の炭化水素基である。）

（式中、Ｒ^７、Ｒ^８、ｅ、ｆ及びｇは上記と同じである。）

（式中、Ｒ^７、ｅ、ｆ及びｇは上記と同じである。） Furthermore, the component (A) is one or more linear polyfluoro compounds selected from the group consisting of the following general formula (4), the following general formula (5) and the following general formula (6) preferable.

(Wherein R ⁷ is, independently of one another, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, e and f each represents an integer of 1 to 150, and the average value of e + f Is 2 to 300, g is an integer of 0 to 6, and R ⁸ is each independently a substituted or unsubstituted monovalent hydrocarbon group.)

(Wherein, R ⁷ , R ⁸ , e, f and g are as defined above)

(Wherein, R ⁷ , e, f and g are as defined above)

  With such component (A), the properties such as heat resistance, light resistance and low temperature properties are well balanced, and a cured product more excellent as a sealing material can be obtained.

（式中、ｈは１〜６の整数であり、ｉは１〜４の整数であり、ｊは１〜４の整数であり、ｈ＋ｉ＋ｊは４〜１０の整数であり、Ｒ^９は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｇは互いに独立して、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｊは互いに独立して、酸素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合したエポキシ基若しくはトリアルコキシシリル基又はその両方である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^９−、−（ＳｉＯ）（Ｇ）Ｒ^９−、及び−（ＳｉＯ）（Ｊ）Ｒ^９−の結合の順番は限定されない。） Moreover, it is preferable that said (D) component is cyclic organopolysiloxane represented by following General formula (7).

(Wherein, h is an integer from 1 to 6, i is an integer from 1 to 4, j is an integer of 1 to 4, h + i + j is an integer of 4 to 10, ^{R 9,} independently from each other G is a monovalent hydrocarbon group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom independently of one another. Epoxy or trialkoxysilyl bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom independently of one another. a group or both, ^{however, -. (SiO) (H} ) R 9 -, - (SiO) (G) R 9 -, and ^{- (SiO) (J) R} 9 - is not limited binding order. )

  If it is such (D) component, the hardened | cured material which shows favorable adhesiveness with respect to various base materials can be obtained.

  Furthermore, the component (F) is preferably liquid at 23 ° C. under normal pressure.

  If it is such (F) component, it is excellent by workability.

（式中、ｋは１〜６の整数、ｌは１〜４の整数、ｍは１〜４の整数、ｋ＋ｌ＋ｍは４〜１０の整数、Ｒ^１０は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｌは互いに独立して、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｍは互いに独立して、２価の炭化水素基を介してケイ素原子に結合した環状無水カルボン酸残基である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^１０−、−（ＳｉＯ）（Ｌ）Ｒ^１０−及び−（ＳｉＯ）（Ｍ）Ｒ^１０−の結合の順番は限定されない。） In addition, the component (F) is preferably a cyclic organopolysiloxane represented by the following general formula (8).

(Wherein k is an integer of 1 to 6; l is an integer of 1 to 4; m is an integer of 1 to 4; k + l + m is an integer of 4 to 10; R ¹⁰ independently of each other is a substituted or unsubstituted monovalent) And L independently represents a monovalent perfluoroalkyl group or monovalent valence bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And M is a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group independently of each other, provided that — (SiO) (H) R ¹⁰ -, - (SiO) (L ) R 10 - and ^{- (SiO) (M) R} 10 - is not limited binding order).

  If it is such (F) component, the hardened | cured material which the adhesiveness with respect to various base materials improved can be obtained.

（式中、ｏは１〜１０の整数である。） Moreover, it is preferable that the said monovalent | monohydric perfluoroalkyl group or monovalent | monohydric perfluorooxyalkyl group is group represented by following General formula (9) or General formula (10) mutually independently.
C _n F _{2n + 1-} (9)
(Wherein n is an integer of 1 to 10)

(In the formula, o is an integer of 1 to 10)

  A monovalent perfluoroalkyl group contained in A in the general formula (1), D in the general formula (2), G in the general formula (7) and L in the general formula (8) or When the monovalent perfluorooxyalkyl group is such, it is possible to obtain a composition having better compatibility with the component (A), dispersibility, and uniformity after curing.

  Moreover, it is preferable that the initial stage transmittance | permeability with respect to the light of the wavelength of 450 nm of the 2 mm thick hardened | cured material obtained by hardening | curing the said curable composition for optical semiconductor sealing is 85.0% or more.

  Thus, if the initial transmittance for light of a wavelength of 450 nm is 85.0% or more, in the optical semiconductor device in which the LED is sealed by the cured product obtained by curing the composition of the present invention, The efficiency with which the light emitted from the light can be extracted to the outside is sufficient.

  Furthermore, it is preferable that the refractive index at 25 ° C., 589 nm (D line of sodium) of the cured product obtained by curing the curable composition for encapsulating an optical semiconductor is 1.30 or more and less than 1.40.

  As described above, when the refractive index is 1.30 or more and less than 1.40, the light emitted from the LED in the optical semiconductor device in which the LED is sealed by the cured product obtained by curing the composition of the present invention The efficiency with which light can be extracted to the outside is preferable because there is no risk of being insufficient due to the design of the optical semiconductor device.

  In addition, the present invention is characterized by comprising an optical semiconductor element, and a cured product obtained by curing the curable composition for optical semiconductor sealing of the present invention for sealing the optical semiconductor element. Provided is an optical semiconductor device.

  The curable composition for encapsulating an optical semiconductor of the present invention can give a cured product which is excellent in heat discoloration resistance and further has low gas permeability. Therefore, the optical semiconductor device in which the optical semiconductor element is sealed with the cured product can suppress the decrease in brightness because the color change of the cured product due to heat is small even if it is turned on for a long time. Moreover, since it becomes difficult for sulfur-type gas to permeate | transmit hardened | cured material, the fall of brightness can be suppressed.

  Moreover, it is preferable that the said optical-semiconductor element is a light emitting diode.

  Thus, the cured product of the curable composition for encapsulating an optical semiconductor according to the present invention can be suitably used as a sealant that particularly protects a light emitting diode.

  The curable composition for encapsulating an optical semiconductor according to the present invention has good heat-resistant discoloration resistance and low gas permeability, by combining the components (A) to (E) and, if necessary, the component (F). Therefore, the optical semiconductor device in which the optical semiconductor element is sealed by the cured product can suppress the decrease in brightness even when it is lighted for a long time. In addition, even when the optical semiconductor device is used in an environment exposed to a sulfur-based gas, the decrease in brightness can be suppressed. Therefore, the cured product is suitable as a sealing material for protecting the LED.

It is a schematic sectional drawing which shows an example of the optical semiconductor device of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor device of this invention.

  Hereinafter, the present invention will be described in more detail.

  As described above, a curable composition for encapsulating an optical semiconductor having good heat-resistance discoloration and low gas permeability, and an optical semiconductor in which an optical semiconductor element is encapsulated by a cured product obtained by curing the composition. An apparatus is required.

  The present inventors diligently studied to achieve the above object. As a result, if it is a composition containing the following components (A) to (E), it becomes a curable composition for encapsulating an optical semiconductor which gives a cured product having good heat discoloration resistance and low gas permeability. The present invention has been completed.

  Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited thereto. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

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

The alkenyl group contained in the component (A) is preferably an alkenyl group having preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and having a CH ₂ CHCH— structure at the end, such as vinyl group and allyl group And propenyl group, isopropenyl group, butenyl group, hexenyl group and the like, among which vinyl group and allyl group are particularly preferable.

  As a perfluoropolyether structure contained in said (A) component, the bivalent perfluoropolyether group represented by following General formula (11) or following General formula (12) is preferable.

  In the above general formula (11), p is 2 or 3, q and s each is preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and the average value of q + s is preferably 2 And more preferably 5 to 200, and r is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

  In the general formula (12), t is preferably 2 or 3, u is preferably an integer of 1 to 300, more preferably an integer of 1 to 200, and v is preferably an integer of 1 to 80, more preferably Preferably, it is an integer of 1 to 50, and the average value of u + v is preferably 2 to 380, more preferably 2 to 250.

  The alkenyl group content in the component (A) is from 0.0050 to 0.200 mol / 100 g, preferably from 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 to cause curing failure, and when the alkenyl group content exceeds 0.200 mol / 100 g, the rubber elastic body of the cured product Mechanical properties may be impaired.

（式中、Ｒ^５及びＲ^６は互いに独立して、アルケニル基、又は、置換若しくは非置換の１価の炭化水素基であり、二つ以上はアルケニル基である。Ｒ^７は互いに独立して、水素原子、又は、置換若しくは非置換の１価の炭化水素基であり、ｅ及びｆはそれぞれ１〜１５０の整数であって、且つｅ＋ｆの平均値は２〜３００であり、ｇは０〜６の整数である。） As a preferable example of (A) component, the linear polyfluoro compound represented by following General formula (3) is mentioned.

(Wherein R ⁵ and R ⁶ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and two or more are an alkenyl group. R ⁷ is independently of each other A hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, e and f each represents an integer of 1 to 150, and the average value of e + f is 2 to 300, and g is 0 to It is an integer of 6.)

Here, examples of the alkenyl group contained in R ⁵ and R ⁶ include the same as above, and examples of the other substituted or unsubstituted monovalent hydrocarbon groups include monovalent groups having 1 to 12 carbon atoms. A hydrocarbon group is preferable, and in particular, a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable, and specifically, alkyl such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group and the like A group; an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group and a phenylethyl group; and a substituted monovalent hydrocarbon having part or all of hydrogen atoms of these groups substituted with a halogen atom such as fluorine Groups and the like. Among them, methyl and ethyl are particularly preferable.

Examples of the substituted or unsubstituted monovalent hydrocarbon group contained in R ⁷ include the same groups as the examples of the substituted or unsubstituted monovalent hydrocarbon group of R ⁵ and R ⁶ described above.

  E and f each are preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and the average value of e + f is preferably 2 to 300, more preferably 2 to 200. Moreover, g is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

  More preferable examples of the component (A) include linear polyfluoro compounds represented by the following general formulas (4) to (6).

In the above general formulas (4) to (6), R ⁷ is the same group as above, and e, f and g are the same as above. R ⁸ is, independently of one another, a substituted or unsubstituted monovalent hydrocarbon group, and the same groups as exemplified for the substituted or unsubstituted monovalent hydrocarbon group of R ⁵ and R ⁶ described above are It can be mentioned.

  The following compounds may be mentioned as specific examples of the linear polyfluoro compound represented by the above general formula (4). Hereinafter, Me represents a methyl group, and Et represents an ethyl group.

（式中、ｅ及びｆは上記と同様である。）

(Wherein e and f are as defined above)

（式中、ｅ及びｆは上記と同様である。） Moreover, as a specific example of the linear polyfluoro compound represented by the said General formula (5), what is represented by a following formula is mentioned.

(Wherein e and f are as defined above)

（式中、ｅ及びｆは上記と同じである。） Furthermore, as a specific example of the linear polyfluoro compound represented by the said General formula (6), what is represented by a following formula is mentioned.

(Wherein e and f are the same as above)

  The viscosity of the component (A) at 23 ° C. is preferably 500 to 100,000 mPa · s, more preferably 1,000 to 50,000 mPa · s, as measured by the viscosity measurement defined in JIS K 7117-1: 1999. It is desirable for the composition of the present invention to be used as a sealing material for LEDs.

  The linear polyfluoro compounds of the component (A) can be used singly or in combination of two or more. That is, among the linear polyfluoro compounds represented by the general formulas (4) to (6), one type may be used alone, or two or more types may be used in combination.

（式中、ａは１〜５０の整数であり、ｂは１〜５０の整数であり、ａ＋ｂは２〜１００の整数であり、Ａは、互いに独立して、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｒ^１は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｒ^２は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｒ^３は互いに独立して置換又は非置換の１価の炭化水素基である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^２−及び−（ＳｉＯ）（Ａ）Ｒ^３−の結合の順番は限定されない。） [(B) component]
The component (B) is an organohydrogenpolysiloxane represented by the following general formula (1), and functions as a crosslinking agent for the component (A). The component (B) also contributes to the low gas permeability of the cured product obtained by curing the composition of the present invention.

(Wherein, a is an integer of 1 to 50, b is an integer of 1 to 50, a + b is an integer of 2 to 100, and A is independently of each other a silicon atom, an oxygen atom or a nitrogen atom And a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain one or more of R ^{1 s} independently of ^one another is substituted or unsubstituted 1 And R ² is independently of each other a substituted or unsubstituted monovalent hydrocarbon group, and R ³ is independently of each other a substituted or unsubstituted monovalent hydrocarbon group. However, the order of bonding of-(SiO) (H) R ^2- and-(SiO) (A) R ^3- is not limited.)

In the above general formula (1), a is an integer of 1 to 50, preferably an integer of 1 to 30, b is an integer of 1 to 50, preferably an integer of 1 to 30, and a + b is 2 to 100 It is an integer, preferably an integer of 2 to 60. However, the order of bonding of-(SiO) (H) R ^2- and-(SiO) (A) R ^3- is not limited.

  Further, A in the above general formula (1) is a monovalent perfluoroalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom independently of each other. Or a monovalent perfluorooxyalkyl group. The A is a group appropriately introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

（式中、ｏは１〜１０の整数、好ましくは２〜８の整数である。） As this monovalent | monohydric perfluoroalkyl group or monovalent | monohydric perfluorooxyalkyl group, group represented by following General formula (9) and (10) is mentioned.
C _n F _{2n + 1-} (9)
(Wherein n is an integer of 1 to 10, preferably an integer of 3 to 7)

(Wherein, o is an integer of 1 to 10, preferably an integer of 2 to 8)

Moreover, as a divalent hydrocarbon group which may connect a silicon atom with a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group and a silicon atom and which may contain a silicon atom, an oxygen atom or a nitrogen atom, it has 2 carbon atoms. Or an alkylene group of 12 to 12 or an ether group, a silicon atom, an amide bond, a divalent aromatic hydrocarbon group, a carbonyl bond or the like interposed in the group, and specific examples thereof include It can be illustrated.

Furthermore, R ¹ in the above general formula (1) is, independently of ^one another, a substituted or unsubstituted monovalent hydrocarbon group, and the substituted or unsubstituted monovalent hydrocarbon group of R ⁵ and R ⁶ described above And the same groups as in the above. Among them, methyl group is particularly preferable.

Further, R ² in the above general formula (1) is, independently of one another, a substituted or unsubstituted monovalent hydrocarbon group, and examples of the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ¹ and Similar groups are mentioned.

Furthermore, R ³ in the above general formula (1) is, independently of one another, a substituted or unsubstituted monovalent hydrocarbon group, and examples of the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ¹ Similar groups are mentioned.

  Specific examples of the organohydrogenpolysiloxane represented by the above general formula (1) include the following compounds. Me is methyl, Et is ethyl, and Ph is phenyl.

  The component (B) may be used alone or in combination of two or more. The compounding amount of the component (B) is silicon contained in the component (B) with respect to 1 mol in total of the alkenyl group of the component (A) and the monovalent unsaturated hydrocarbon group of the component (E) described later. The amount is 0.50 to 2.0 moles, more preferably 0.80 to 1.5 moles of hydrogen atoms directly bonded to the atoms. If the hydrogen atom directly bonded to the silicon atom is less than 0.50 mol, the degree of crosslinking may be insufficient. If it is more than 2.0 mol, the storage stability of the composition of the present invention may be impaired. is there.

[(C) ingredient]
The platinum group metal catalyst, which is the component (C) of the present invention, is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst comprises an alkenyl group and a monovalent unsaturated hydrocarbon group contained in the composition, particularly an alkenyl group in component (A), and an SiH group contained in the composition, B) A catalyst which promotes the addition reaction with the SiH group in the component. Since this hydrosilylation reaction catalyst is generally a noble metal or a compound thereof and is expensive, platinum or a platinum compound relatively easily available is often used.

Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, metal platinum supported on silica, alumina, carbon or the like. Rhodium, ruthenium, iridium and palladium compounds are also known as platinum group metal catalysts other than platinum or their compounds, and examples thereof include RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ ( CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like can be exemplified. In the above formulae, Ph represents a phenyl group.

  When using these catalysts, it is possible to use them in solid form when they are solid catalysts, but in order to obtain a more uniform cured product, chloroplatinic acid or complex, for example, toluene, ethanol etc. It is preferable to use one dissolved in a suitable solvent of the above in a state of being compatible with the linear polyfluoro compound of the component (A).

  The compounding amount of the component (C) is an effective amount as a hydrosilylation reaction catalyst, and is preferably 0.1 to 500 ppm, particularly preferably 0.5 to 200 ppm based on 100 parts by mass of the component (A). Although it is mass conversion, it can be appropriately increased or decreased according to the desired curing rate.

[(D) component]
The component (D) of the present invention is a monovalent compound bonded to a silicon atom via a hydrogen atom directly bonded to a silicon atom in one molecule, and a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. Organoalkyl group having a perfluoroalkyl group or a monovalent perfluorooxyalkyl group of the above, and an epoxy group or a trialkoxysilyl group or both of which is bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom It is a polysiloxane and has a function as an adhesion-imparting agent which imparts self-adhesiveness to a cured product obtained by curing the composition of the present invention.

（式中、ｈは１〜６の整数であり、ｉは１〜４の整数であり、ｊは１〜４の整数であり、ｈ＋ｉ＋ｊは４〜１０の整数であり、Ｒ^９は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｇは互いに独立して、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｊは互いに独立して、酸素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合したエポキシ基若しくはトリアルコキシシリル基又はその両方である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^９−、−（ＳｉＯ）（Ｇ）Ｒ^９−、及び−（ＳｉＯ）（Ｊ）Ｒ^９−の結合の順番は限定されない。） As organopolysiloxane as the component (D), cyclic organopolysiloxanes represented by the following general formula (7) are preferable.

(Wherein, h is an integer from 1 to 6, i is an integer from 1 to 4, j is an integer of 1 to 4, h + i + j is an integer of 4 to 10, ^{R 9,} independently from each other G is a monovalent hydrocarbon group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom independently of one another. Epoxy or trialkoxysilyl bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom independently of one another. a group or both, ^{however, -. (SiO) (H} ) R 9 -, - (SiO) (G) R 9 -, and ^{- (SiO) (J) R} 9 - is not limited binding order. )

In the above general formula (7), h is an integer of 1 to 6, preferably an integer of 1 to 5, i is an integer of 1 to 4, preferably an integer of 1 to 3, and j is an integer of 1 to 4, preferably The integer of 1-3, h + i + j is an integer of 4-10, Preferably it is an integer of 4-8. ^{However, - (SiO) (H)} R 9 -, - (SiO) (G) R 9 - and ^{- (SiO) (J) R} 9 - bond order is not limited.

Also, R ⁹ is a monovalent hydrocarbon group independently substituted or unsubstituted with one another, include the exemplified the same groups for R ¹ described above.

  Furthermore, G is independently of each other a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And the same groups as the examples of A described above. This G is a group suitably introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

Further, J is, independently of each other, an epoxy group or a trialkoxysilyl group or both of which is bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom. As such an epoxy group, for example, those represented by the following general formula (13) can be mentioned.

In the above general formula (13), R ¹¹ may be an oxygen atom, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and specifically, methylene Groups, alkylene groups such as ethylene group, propylene group, butylene group, hexylene group and octylene group, cycloalkylene groups such as cyclohexylene group, and oxyalkylene groups such as oxyethylene group, oxypropylene group and oxybutylene group Be

Specific examples of such epoxy groups include those shown below.

On the other hand, as said trialkoxy silyl group, what is represented by following General formula (14) is mentioned, for example.

In the above general formula (14), R ¹² is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and specifically, methylene, ethylene, propylene, butylene And alkylene groups such as hexylene, cyclohexylene and octylene. Further, R ¹³ is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and specifically, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, etc. It can be mentioned.

Specific examples of such trialkoxysilyl groups include those shown below.

  Examples of such component (D) include the following compounds. Me is methyl and Et is ethyl.

  The component (D) may be used alone or in combination of two or more. The amount of component (D) used 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 component (A). If the amount is less than 0.10 parts by mass, sufficient adhesion may not be obtained, and if it exceeds 10.0 parts by mass, the physical strength of the cured product obtained by curing the composition of the present invention decreases. There is a risk of

（式中、ｃは１〜４の整数、ｄは３〜６の整数、ｃ＋ｄは４〜１０の整数、Ｒ^４は置換又は非置換の１価の炭化水素基、Ｄは酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基、Ｅはケイ素原子に直結した１価の不飽和炭化水素基である。ただし、−（ＳｉＯ）（Ｄ）Ｒ^４−及び−（ＳｉＯ）（Ｅ）Ｒ^４−の結合の順番は限定されない。） [(E) ingredient]
The component (E) of the present invention is a bivalent compound represented by the following general formula (2), which may contain an oxygen atom or a nitrogen atom and a monovalent unsaturated hydrocarbon group directly bonded to a silicon atom in one molecule. A cyclic organopolysiloxane having a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a hydrocarbon group of the following: and a cured product obtained by curing the composition of the present invention It contributes to the heat discoloration resistance of the object.

(Wherein, c is an integer of 1 to 4; d is an integer of 3 to 6; c + d is an integer of 4 to 10; R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group; D is an oxygen atom or a nitrogen atom Or a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain at least one substituent, and E is a monovalent unsaturated hydrocarbon group directly bonded to a silicon atom However, the order of bonding of-(SiO) (D) R ^4- and-(SiO) (E) R ^4- is not limited.)

  In the above general formula (2), c is an integer of 1 to 4, preferably an integer of 1 to 3, d is an integer of 3 to 6, preferably an integer of 3 to 5, and c + d is an integer of 4 to 10, preferably It is an integer of 4-8.

Further, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the same groups as the examples of the substituted or unsubstituted monovalent hydrocarbon group of R ¹ described above.

  Furthermore, D is a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom, and The same groups as the examples can be mentioned. This D is a group introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

  E is a monovalent unsaturated hydrocarbon group directly linked to a silicon atom, and specific examples thereof include unsaturated chain hydrocarbon groups such as vinyl group, allyl group, butenyl group, hexenyl group and decenyl group. Be Among these, a vinyl group or an allyl group is preferable.

Examples of such component (E) include the following compounds. In the following formulas, Me represents a methyl group.

  The component (E) may be used alone or in combination of two or more. The amount of component (E) used is in the range of 0.50 to 30.0 parts by mass, preferably 1.0 to 20.0 parts by mass, per 100 parts by mass of component (A). If it is less than 0.50 parts by mass, the effect of improving the heat-resistant discoloration of the cured product obtained by curing the composition of the present invention may not be sufficiently obtained, and if it exceeds 30.0 parts by mass The gas permeability of the cured product obtained by curing the composition of the present invention may be significantly increased.

[(F) component]
It is preferable that the curable composition for optical semiconductor sealing of this invention is what contains the following (F) component as an arbitrary component. The component (F) of the present invention is a carboxylic acid anhydride, which improves the adhesion imparting ability of the component (D) and promotes the development of self-adhesiveness of a cured product obtained by curing the composition of the present invention. It is for. As the component (F), any of those used as a curing agent for epoxy resins can be used.

  The component (F) is preferably a liquid at 23 ° C. under normal pressure. If it is such (F) component, it is excellent by workability.

（式中、ｋは１〜６の整数、ｌは１〜４の整数、ｍは１〜４の整数、ｋ＋ｌ＋ｍは４〜１０の整数、Ｒ^１０は互いに独立して置換又は非置換の１価の炭化水素基であり、Ｌは互いに独立して、ケイ素原子、酸素原子又は窒素原子を含んでも良い２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｍは互いに独立して、２価の炭化水素基を介してケイ素原子に結合した環状無水カルボン酸残基である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^１０−、−（ＳｉＯ）（Ｌ）Ｒ^１０−及び−（ＳｉＯ）（Ｍ）Ｒ^１０−の結合の順番は限定されない。） Furthermore, as said (F) component, cyclic organopolysiloxane represented by following General formula (8) is preferable.

(Wherein k is an integer of 1 to 6; l is an integer of 1 to 4; m is an integer of 1 to 4; k + l + m is an integer of 4 to 10; R ¹⁰ independently of each other is a substituted or unsubstituted monovalent) And L independently represents a monovalent perfluoroalkyl group or monovalent valence bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And M is a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group independently of each other, provided that — (SiO) (H) R ¹⁰ -, - (SiO) (L ) R 10 - and ^{- (SiO) (M) R} 10 - is not limited binding order).

In the above general formula (8), k is an integer of 1 to 6, preferably an integer of 1 to 5, l is an integer of 1 to 4, preferably an integer of 1 to 3, and m is an integer of 1 to 4, preferably The integer of 1 to 3 and k + 1 + m are an integer of 4 to 10, preferably an integer of 4 to 8. ^{However, - (SiO) (H)} R 10 -, - (SiO) (L) R 10 - and ^{- (SiO) (M) R} 10 - is not limited binding order.

Further, R ¹⁰ is a monovalent hydrocarbon group independently substituted or unsubstituted with one another, include the exemplified the same groups for R ¹ described above.

  Furthermore, L is, independently of each other, a monovalent perfluoroalkyl group or monovalent perfluorooxy group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. Examples of the alkyl group include the same groups as the examples of A described above. This L is a group suitably introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

Further, M is a cyclic carboxylic acid anhydride residue bonded to a silicon atom independently of each other via a divalent hydrocarbon group, and specific examples thereof include a group represented by the following general formula (15) .

In the above general formula (15), R ¹⁴ is preferably a divalent hydrocarbon group having a carbon number of 1 to 15, and specific examples thereof include a methylene group, an ethylene group, a propylene group and a butylene group. Or a propylene group is particularly preferred.

  Examples of the component (F) represented by the above general formula (8) include the following compounds. Me is methyl and Et is ethyl.

The component (F) may be used alone or in combination of two or more.
The compounding quantity of the said (F) component in the case of including the said (F) component is 0.010-5.0 mass parts with respect to 100 mass parts of (A) components, Preferably 0.10-3.0 mass The scope of the department. In the case of 0.010 parts by mass or more, an effect sufficient to accelerate the development of adhesiveness of the composition of the present invention can be obtained, and in the case of 5.0 parts by mass or less, the composition of the present invention is cured. There is no risk that the transmittance of the resulting cured product to light at a wavelength of 450 nm will be impaired.

[Other ingredients]
In addition to the components (A) to (E) and the optional component (F), in the curable composition for encapsulating an optical semiconductor of the present invention, a plasticizer, a viscosity, and the like, in order to enhance its practicality. Various additives such as a modifier, a flexibility imparting agent, an inorganic filler, a reaction control agent, and an adhesion promoter other than the component (F) can be added as necessary. The blending amount of these additives is optional.

A polyfluoromonoalkenyl compound represented by the following general formula (16) and / or a linear polyrepresented by the following general formulas (17) and (18) as a plasticizer, a viscosity modifier, and a flexibility imparting agent Fluoro compounds can be used in combination.
_{Rf- (Q) w -CH = CH} 2 (16)
[Wherein, R f is a group represented by the following general formula (19),
_{F- [CF (CF 3) CF} 2 O] x -C y F 2y - (19)
(In the formula, x is preferably an integer of 1 to 200, more preferably 1 to 150, and y is preferably an integer of 1 to 3).
Q is -CH _2- , -OCH _2- , -CH ₂ OCH ₂ -or -CO-NR ¹⁵ -T- (wherein R ¹⁵ is a hydrogen atom, a methyl group, a phenyl group or an allyl group, and T is- CH _2- , a group represented by the following structural formula (20) or a group represented by the following structural formula (21)), w is 0 or 1. ]

_{X'-O- (CF 2 CF 2} CF 2 O) z -X '(17)
( _Wherein , X ′ is a group represented by C _{s ′} F _{2 s ′ + 1} − (s ′ is 1 to 3), and z is preferably an integer of 1 to 200, more preferably an integer of 2 to 100 is there.)
_{X'-O- (CF 2 O)} t '(CF 2 CF 2 O) u' -X '(18)
(Wherein, X ′ is the same as above, and t ′ and u ′ are each preferably an integer of 1 to 200, more preferably an integer of 1 to 100, and the average value of t ′ + u ′ is preferably Is 2 to 400, more preferably 2 to 300.)

  As a specific example of the polyfluoro mono alkenyl compound represented by the said General formula (16), the following are mentioned, for example. In addition, Me shows a methyl group.

（ここで、ｚ’＝１〜１００である。）

(Here, z '= 1 to 100.)

As a specific example of the linear polyfluoro compound represented by the said General Formula (17) and (18), the following are mentioned, for example.
_{CF 3 O- (CF 2 CF 2} CF 2 O) v '-CF 2 CF 3
CF ₃ -[(OCF ₂ CF ₂ ) _{w '} (OCF ₂ ) _x' ] -O-CF ₃
(Here, v ′, w ′ and x ′ each are preferably an integer of 1 to 200, more preferably an integer of 1 to 150, and the average value of w ′ + x ′ is preferably an integer of 2 to 400, more preferably Preferably it is an integer of 2 to 300.)

  Further, the viscosity (23 ° C.) of the polyfluoro compound represented by the above general formulas (16) to (18) is 5.00 to 100,000 mPa · s, particularly 50, by the same measuring method as the component (A). It is desirable that it is in the range of from 0 to 50,000 mPa · s.

  Examples of the inorganic filler include fumed silica, precipitated silica, spherical silica, silica powder such as silica airgel, or the surface of the silica powder treated with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, etc. The surface-treated silica powder further comprises a monovalent perfluoroalkyl group represented by the general formula (9) or a monovalent perfluorooxyalkyl group represented by the general formula (10). Silica-based reinforcing filler such as silica powder reprocessed with organosilane or organosiloxane, reinforcing or semi-reinforcing filler such as quartz powder, fused quartz powder, diatomaceous earth, calcium carbonate etc., titanium oxide, iron oxide, Inorganic pigments such as carbon black and cobalt aluminate, titanium oxide, iron oxide, carbon black, cerium oxide, Heat resistance improver such as cerium oxide, zinc carbonate, magnesium carbonate and manganese carbonate, thermal conductivity imparting agent such as alumina, boron nitride, silicon carbide and metal powder, conductivity impartation such as carbon black, silver powder and conductive zinc flower Agents and the like. In addition, inorganic substances such as magnesium fluoride, aluminum fluoride, calcium fluoride, lithium fluoride, sodium fluoride, thorium fluoride silicon oxide, etc. having a refractive index of 1.50 or less at 25 ° C., 589 nm (sodium D line) Microparticles are also useful as reinforcing fillers.

  Examples of control agents for hydrosilylation reaction catalyst include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl Acetylenic alcohols such as -1-pentyn-3-ol, phenylbutynol and the like, and chlorosilanes having a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group similar to A described above and an acetylenic alcohol Reactants, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene-1-yne, triallylisocyanurate etc., or polyvinyl siloxane, organic phosphorus compound etc. are mentioned, and the addition thereof Curing reactivity and storage stability can be maintained at an appropriate level.

  Examples of the adhesion promoter other than the component (F) include organic zirconium compounds such as zirconium alkoxide and zirconium chelate, and organic titanium compounds such as titanium alkoxide and titanium chelate.

  The method for producing the curable composition for encapsulating an optical semiconductor according to the present invention is not particularly limited, and the components (A) to (E), an optional component (F) and other optional components are mixed to produce the curable composition for optical semiconductor encapsulation. can do. In that case, as needed, mixing apparatuses, such as a planetary mixer, a Ross mixer, a Hobart mixer, and kneaders, such as a kneader and 3 rolls, can be used.

  With regard to the constitution of the curable composition for encapsulating an optical semiconductor according to the present invention, the above components (A) to (E), an optional component (F) and all other optional components in one composition according to the application It may be configured as a so-called one-component type to be handled as, or may be configured as a two-component type, and both may be mixed at the time of use.

  The curable composition for encapsulating an optical semiconductor of the present invention is cured by heating to give a cured product having good heat-resistant discoloration and low gas permeability, such as LED, IC, LSI, organic EL, etc. It is useful as a sealing material which protects an optical semiconductor element etc. Although the curing temperature of the curable composition for encapsulating an optical semiconductor is not particularly limited, it is generally 20 to 250 ° C., preferably 40 to 200 ° C. In addition, the curing time in that case may be appropriately selected as the time for completing the crosslinking reaction and the adhesion reaction with various semiconductor package materials, but generally 10 minutes to 10 hours are preferable, and 30 minutes to 8 hours are more preferable. preferable.

  The transmittance of light having a wavelength of 450 nm after leaving a 2 mm-thick cured product obtained by curing the composition of the present invention at 150 ° C. for 1,000 hours is at least 90.0%, preferably 92, initially. .0% or more. When the transmittance is less than the initial 90.0%, the brightness may decrease significantly with time when the optical semiconductor device in which the optical semiconductor element is sealed by the cured product is lighted for a long period of time There is.

The water vapor permeability of a 1 mm thick cured product obtained by curing the composition of the present invention is 20.0 g / m ² · day or less, preferably 15.0 g / m ² · day or less. When it exceeds 20.0 g / m ² · day, the periphery of the LED is plated with silver, and the optical semiconductor device in which the LED is sealed with a cured product obtained by curing the composition of the present invention is a sulfur-based gas When exposed, silver may be blackened by the gas and the brightness may be reduced. In addition, the said water-vapor-permeation rate is the value measured using L80-5000 type water-vapor-permeability meter by Lyssy company based on JISK7129: 2008.

  Furthermore, the initial transmittance of light having a wavelength of 450 nm of the 2 mm thick cured product obtained by curing the composition of the present invention is 85.0% or more, preferably 87.0% or more. When the transmittance is 85.0% or more, the efficiency with which the light emitted from the LED chip can be extracted to the outside is sufficient in the optical semiconductor device in which the optical semiconductor element is sealed by the cured product.

  Furthermore, the refractive index at 25 ° C., 589 nm (D line of sodium) of the cured product obtained by curing the composition of the present invention is preferably 1.30 or more and less than 1.40. When the refractive index is within this range, in the optical semiconductor device in which the optical semiconductor element is sealed by the cured product, the efficiency with which the light emitted from the LED chip can be extracted to the outside is the design of the optical semiconductor device It is preferable because there is no fear of lowering due to

  In addition, when using the composition of this invention, according to the use and the objective, according to the use and the objective, this composition is a suitable fluorinated solvent, such as 1,3-bis (trifluoromethyl) benzene, Fluorinert (manufactured by 3M), Per It may be used by dissolving it in a desired concentration in fluorobutyl methyl ether, perfluorobutyl ethyl ether or the like.

  Thus, if it is the curable composition for optical semiconductor sealing which has said (A)-(E) component, (F) component which is an arbitrary component, and other arbitrary components, and has said characteristics, it is favorable. It is possible to obtain a cured product having heat discoloration resistance and low gas permeability.

  The structure of the optical semiconductor device which can use the curable composition for optical semiconductor sealing of this invention is not specifically limited. The optical semiconductor device of the present invention comprises an optical semiconductor element and a cured product obtained by curing the curable composition for optical semiconductor sealing of the present invention for sealing the optical semiconductor element. Typical cross sectional structures are shown in FIGS. 1 and 2.

  In the optical semiconductor device (light emitting device) 10 shown in FIG. 1, a cone-shaped recess 2 'is formed in the tip 2a of the first lead frame 2 so that the hole diameter gradually increases upward from the bottom thereof. The LED chip 1 is connected and fixed on the bottom surface of the LED chip 1 by silver bonding or the like by die bonding, whereby the first lead frame 2 and one electrode (not shown) of the bottom surface of the LED chip 1 are electrically connected. ing. The bottom of the recess 2 'is plated with silver. Further, the tip 3a of the second lead frame 3 and the other electrode (not shown) on the upper surface of the LED chip 1 are electrically connected through the bonding wire 4.

  Furthermore, the LED chip 1 is covered with the sealing material 5 made of a cured product obtained by curing the curable composition for encapsulating an optical semiconductor of the present invention in the recess 2 '.

  In addition, the LED chip 1, the tip 2a of the first lead frame 2 and the upper end of the terminal 2b, and the tip 3a of the second lead frame 3 and the upper end of the terminal 3b have a light transmission having a convex lens 6 at the tip. It is covered and sealed by the resin part 7. 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 to the outside.

  In the optical semiconductor device (light emitting device) 10 'of FIG. 2, a mortar-shaped recess 8' is formed on the top of the package substrate 8 so that the hole diameter gradually spreads upward from the bottom and on the bottom of the recess 8 '. The LED chip 1 is bonded and fixed by a die bonding material, and the electrode of the LED chip 1 is electrically connected to the electrode 9 provided on the package substrate 8 by the bonding wire 4. The bottom of the recess 8 'is plated with silver.

  Furthermore, in the recess 8 ′, the LED chip 1 is covered with the sealing material 5 made of a cured product obtained by curing the curable composition for encapsulating an optical semiconductor of the present invention.

  Here, for the LED chip 1, without particular limitation, a light emitting element used for a conventionally known LED chip can be used. As such a light emitting element, a semiconductor material is formed by laminating a semiconductor material on a substrate provided with a buffer layer of GaN, AlN or the like as needed by various methods such as MOCVD method, HDVPE method, liquid phase growth method, for example. The thing is mentioned. Although various materials can be used as the substrate in this case, for example, sapphire, spinel, SiC, Si, ZnO, GaN single crystal and the like can be mentioned. Among these, it is preferable to use sapphire from the viewpoint of being able to easily form GaN with good crystallinity and having a high industrial utility value.

Examples of semiconductor materials to be stacked include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN, SiC and the like. Among these, nitride-based compound semiconductors (In _x Ga _y Al _z N) are preferable from the viewpoint of obtaining high luminance. Such materials may include activators and the like.

  Examples of the structure of the light emitting element include a MIS junction, a pn junction, a homo junction having a PIN junction, a hetero junction, a double hetero structure, and the like. Moreover, it can also be made into a single or multiple quantum well structure.

  The light emitting element may or may not be provided with a passivation layer.

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

  A single type of light emitting element may be used to emit single color light, or a plurality of light emitting elements may be used to emit single color light or multiple colors.

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

  The electrode on the light emitting element can be electrically connected to the lead terminal or the like by various methods. As the electrical connection member, one having good ohmic mechanical connectivity with the electrode of the light emitting element, etc. is preferable, and, for example, gold, silver, copper, platinum, aluminum or the like as described in FIG. 1 and FIG. The bonding wire 4 using an alloy etc. is mentioned. In addition, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can also be used. Among these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

  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 translucent resin portion 7 is not particularly limited as long as it is a material having translucency, but an epoxy resin or a silicone resin is mainly used.

  Further, the package substrate 8 can be manufactured using various materials. For example, polyphthalic acid amide (PPA), polycarbonate resin, polyphenylene sulfide resin, polybutylene terephthalate resin, polyamide resin, liquid crystal polymer, epoxy resin, acrylic Resin, silicone resin, modified silicone resin, ABS resin, BT resin, ceramic etc. are mentioned. Among these, polyphthalic acid amide (PPA) is particularly preferable from the viewpoint of heat resistance, strength and cost. Further, the package substrate 8 is preferably mixed with a white pigment such as barium titanate, titanium oxide, zinc oxide or barium sulfate to improve the light reflectance.

  Next, the sealing material 5 for covering the LED chip 1 efficiently transmits the light from the LED chip 1 to the outside, and protects the LED chip 1 and the bonding wires 4 from external force, dust and the like. is there. As the sealing material 5, a cured product of the composition of the present invention is used. The sealing material 5 may contain a fluorescent material, a light diffusion member, and the like.

  The curable composition for encapsulating an optical semiconductor according to the present invention can give a cured product having good heat resistance and low gas permeability, and therefore, an optical semiconductor device in which a photosemiconductor element is sealed by the cured product. Since the discoloration of the cured product due to heat is small even when the lamp is lighted for a long time, it is possible to suppress the decrease in brightness. Furthermore, even when used under an environment exposed to a sulfur-based gas, the sulfur-based gas hardly permeates the cured product, so that it is possible to suppress the decrease in brightness. Therefore, the curable composition for optical semiconductor sealing of this invention can be suitably used as a sealing material for protecting LED from the above characteristics which a hardened | cured material has.

  EXAMPLES Hereinafter, the present invention will be more specifically described by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, Me shows a methyl group.

（ただし、ａ’及びｂ’は１以上の整数であり、ａ’＋ｂ’の平均値は３５である。）

（ただし、ｃ’及びｄ’は１以上の整数であり、ｃ’の平均値は８であり、ｄ’の平均値は３である。）

Example 1
100 parts by mass of a linear polyfluoro compound (viscosity 4,010 mPa · s, vinyl group weight 0.0299 mol / 100 g) represented by the following formula (22): a solution of platinum-divinyl tetramethyl disiloxane complex in toluene (platinum 0.20 parts by mass of a concentration of 0.5% by mass, 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, organohydrogenpolysiloxane represented by the following formula (23) .00428 mol / g) 8.65 parts by mass, 2.0 parts by mass of organopolysiloxane represented by the following formula (24), cyclic organopolysiloxane represented by the following formula (25) (vinyl group content 0.00357 mol / g) 2.0 parts by weight were sequentially added and mixed to be uniform. Thereafter, the composition was prepared by degassing operation.

(However, a ′ and b ′ are integers of 1 or more, and the average value of a ′ + b ′ is 35.)

(However, c ′ and d ′ are integers of 1 or more, the average value of c ′ is 8, and the average value of d ′ is 3.)

（ただし、ｅ’及びｆ’は１以上の整数であり、ｅ’＋ｆ’の平均値は３５である。）

（ただし、ｇ’及びｈ’は１以上の整数であり、ｇ’の平均値は１１であり、ｈ’の平均値は３である。）

(Example 2)
100 parts by mass of a linear polyfluoro compound (viscosity 4,050 mPa · s, vinyl group content: 0.0601 mol / 100 g) represented by the following formula (26): a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum 0.20 parts by mass of a concentration of 0.5% by mass, 0.15 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, an organohydrogenpolysiloxane represented by the following formula (27) .00636 mol / g 13.0 parts by mass, 2.5 parts by mass of organopolysiloxane represented by the following formula (28), cyclic organopolysiloxane represented by the following formula (29) (vinyl group content 0.00451 mol / g g) 5.0 parts by mass were sequentially added and mixed to be uniform. Thereafter, the composition was prepared by degassing operation.

(However, e ′ and f ′ are integers of 1 or more, and the average value of e ′ + f ′ is 35.)

(However, g ′ and h ′ are integers of 1 or more, the average value of g ′ is 11, and the average value of h ′ is 3.)

（ただし、ｉ’及びｊ’は１以上の整数であり、ｉ’＋ｊ’の平均値は３５である。）

（ただし、ｋ’及びｌ’は１以上の整数であり、ｋ’の平均値は７であり、ｌ’の平均値は３である。）

(Example 3)
100 parts by mass of a linear polyfluoro compound (viscosity 4,080 mPa · s, vinyl group weight: 0.0899 mol / 100 g) represented by the following formula (30): a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum 0.25 parts by mass of a concentration of 0.5% by mass, 0.15 parts by mass of a 60% solution of 1-ethynyl-1-hydroxycyclohexane in toluene, organohydrogenpolysiloxane represented by the following formula (31) .00499 mol / g 26.1 parts by mass, 2.0 parts by mass of organopolysiloxane represented by the following formula (32), 1.5 parts by mass of organopolysiloxane represented by the following formula (33), the above formula (25) 8.0 parts by weight of the cyclic organopolysiloxane represented by) was sequentially added and mixed to be uniform. Thereafter, the composition was prepared by degassing operation.

(However, i 'and j' are integers of 1 or more, and the average value of i '+ j' is 35.)

(However, k ′ and l ′ are integers of 1 or more, the average value of k ′ is 7, and the average value of l ′ is 3.)

（ただし、ｍ’及びｎ’は１以上の整数であり、ｍ’の平均値は１１であり、ｎ’の平均値は３である。）

(Example 4)
In 50.0 parts by mass of the linear polyfluoro compound represented by the above formula (22), 50.0 parts by mass of the linear polyfluoro compound represented by the above formula (26), platinum-divinyltetramethyldisiloxane complex 0.30 parts by mass of a toluene solution (platinum concentration 0.5 mass%), 0.15 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, an organohydrogenpolysiloxane represented by the following formula (34) 20.6 parts by mass of SiH group content 0.00516 mol / g, 2.0 parts by mass of organopolysiloxane represented by the above formula (24), 2.0 parts by mass of organopolysiloxane represented by the above formula (28), 12.0 parts by mass of a cyclic organopolysiloxane (vinyl group content: 0.00432 mol / g) represented by the following formula (35) is sequentially added to be uniform Engaged. Thereafter, the composition was prepared by degassing operation.

(However, m 'and n' are integers greater than or equal to 1, the average value of m 'is 11, and the average value of n' is 3.)

(Example 5)
In 50.0 parts by mass of the linear polyfluoro compound represented by the above formula (26), 50.0 parts by mass of the linear polyfluoro compound represented by the above formula (30), platinum-divinyltetramethyldisiloxane complex 0.35 parts by mass of a toluene solution (platinum concentration 0.5 mass%), 0.15 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, organohydrogenpolysiloxane 22 represented by the above formula (27) .2 parts by mass, 3.5 parts by mass of the organopolysiloxane represented by the above formula (24), and 15.0 parts by mass of the cyclic organopolysiloxane represented by the above formula (25) are sequentially added and mixed to be uniform did. Thereafter, the composition was prepared by degassing operation.

(Example 6)
In 20.0 parts by mass of the linear polyfluoro compound represented by the above formula (22), 80.0 parts by mass of the linear polyfluoro compound represented by the above formula (30), platinum-divinyltetramethyldisiloxane complex 0.40 parts by mass of a toluene solution (platinum concentration 0.5% by mass), 0.15 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, organohydrogenpolysiloxane 43 represented by the above formula (23) .1 part by mass, 2.0 parts by mass of organopolysiloxane represented by the above formula (32), 2.0 parts by mass of organopolysiloxane represented by the above formula (33), cyclic organopolyester represented by the following formula (36) 20.0 parts by mass of siloxane (vinyl group content: 0.00533 mol / g) was sequentially added and mixed uniformly. Thereafter, the composition was prepared by degassing operation.

(Example 7)
In 2.00 parts by mass of the linear polyfluoro compound represented by the above formula (22), 8.00 parts by mass of the linear polyfluoro compound represented by the above formula (26), a straight chain represented by the above formula (30) 90.0 parts by mass of linear polyfluoro compound, 0.50 parts by mass of a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5 mass%), 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane 0.15 parts by mass, 26.2 parts by mass of organohydrogenpolysiloxane represented by the above formula (27), 1.5 parts by mass of organopolysiloxane represented by the above formula (24), represented by the following formula (37) 2.0 parts by mass of organopolysiloxane and 25.0 parts by mass of cyclic organopolysiloxane represented by the above formula (25) were sequentially added and mixed to be uniform Thereafter, the composition was prepared by degassing operation.

(Example 8)
A composition was prepared in the same manner as in Example 3 except that 0.80 parts by mass of a carboxylic acid anhydride represented by the following formula (38) was added.

(Example 9)
A composition was prepared in the same manner as in Example 5 except that 1.0 part by mass of a carboxylic acid anhydride represented by the following formula (39) was added.

(Comparative example 1)
In Example 3 above, the amount of the organohydrogenpolysiloxane (having an SiH group content of 0.00499 mol / g) represented by the above formula (31) is changed to 19.8 parts by mass to further add the above formula (25) The composition was prepared in the same manner as in Example 3 except that the cyclic organopolysiloxane shown in the above was not added.

(Comparative example 2)
In Example 7 above, the addition amount of the organohydrogenpolysiloxane represented by the above formula (27) is changed to 31.6 parts by mass, and the addition amount of the cyclic organopolysiloxane represented by the above formula (25) is further modified. A composition was prepared in the same manner as in Example 7 except that the amount was changed to 35.0 parts by mass.

(Comparative example 3)
In Example 3 above, the organohydrogenpolysiloxane represented by the above formula (31) was added to 33.1 parts by mass of a cyclic organopolysiloxane represented by the following formula (40) (SiH content: 0.00394 mol / g) A composition was prepared as in Example 3 except that it was changed.

(Comparative example 4)
In Example 3 above, the organohydrogenpolysiloxane represented by the above formula (31) was changed to 40.8 parts by mass of an organohydrogensiloxane (having an amount of SiH groups of 0.00319 mol / g) represented by the following formula (41) The composition was prepared in the same manner as Example 3 except for the above.

（ただし、ｏ’は１以上の整数であり、ｏ’の平均値は８である。） (Comparative example 5)
In Example 3 above, the organohydrogenpolysiloxane represented by the above formula (31) was changed to 21.8 parts by mass of an organohydrogenpolysiloxane (having a SiH group content of 0.00599 mol / g) represented by the following formula (42) A composition was prepared as in Example 3 except that it was changed.

(However, o 'is an integer of 1 or more, and the average value of o' is 8.)

(Comparative example 6)
A composition was prepared in the same manner as in Example 9 except that the cyclic organopolysiloxane represented by the above formula (25) was not added.

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

  1.450 nm light transmittance: A sheet-like cured product having a thickness of 2 mm is prepared, and an initial stage for light of 450 nm is produced using an ultraviolet-visible-near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation). The transmittance (%) was measured. Next, the cured product was left to stand at 150 ° C. for 1,000 hours, and then the transmittance (%) to light of 450 nm was measured again to calculate an initial ratio. The higher the initial ratio, the smaller the color change of the cured product. The results are shown in Table 1.

  2. A sheet-like cured product having a refractive index of 2 mm is prepared, and a multiwavelength Abbe refractometer DR-M2 / 1550 (manufactured by Atago Co., Ltd.) defined in JIS K 0062: 1992 at 25 ° C., 589 nm (sodium The refractive index at line D) was measured. The results are shown in Table 2.

3. Water vapor transmission rate: A sheet-like cured product having a thickness of 1 mm was prepared, and was measured using a Lyssy L80-5000 water vapor permeability meter according to JIS K 7129: 2008. The measurement temperature is 40 ° C., and the area of the cured product used for the measurement is 50 cm ² . The results are shown in Table 2.

  4. Adhesion to polyphthalic acid amide (PPA): two 100 mm × 25 mm test panels of PPA are overlaid with a layer of the above obtained composition 80 μm thick so that the ends overlap by 10 mm The composition was cured by heating at 150 ° C. for 5 hours to produce an adhesive test piece. Subsequently, a tensile shear adhesion test (tensile speed 50 mm / min) was performed on this test piece to evaluate the adhesive strength (shear adhesion) and the cohesive failure rate. The results are shown in Table 2.

  5. Heat-resistant discoloring property of cured product: In the optical semiconductor device having the same configuration as that of the embodiment of FIG. 2, the LED chip 1 emitting light at 450 nm is dipped in the composition obtained above to form the sealing material 5 Thus, an optical semiconductor device in which the LED chip 1 was sealed with a cured product of the composition was fabricated by injecting the solution into the recess 8 ′ and heating for 5 hours at 150 ° C. Then, assuming that the initial brightness when the optical semiconductor device was turned on was 100%, the maintenance ratio of the brightness when continuously turned on for 1,000 hours was determined. The results are shown in Table 2.

  6. Gas Permeability of Cured Product: The optical semiconductor device produced in the same manner as the above “5. Heat-resistant color change property of cured product” is left in a hydrogen sulfide gas atmosphere of 5 ppm at 100 ° C. for 200 hours, The degree of discoloration of silver on the bottom was visually confirmed. The results are shown in Table 2.

  From the results of Tables 1 and 2, the cured product obtained by curing the curable composition for encapsulating an optical semiconductor of the present invention (Examples 1 to 9) has better heat resistance than Comparative Examples 1 to 6 Because of the color change and low gas permeability, no significant decrease in brightness during long-time lighting or color change of silver was observed. On the other hand, in Comparative Examples 1, 2 and 6, since the component (E) did not satisfy the requirements of the present invention, the brightness during long-time lighting was significantly reduced, and discoloration of silver was observed. Moreover, since the (B) component did not satisfy | fill the requirements of this invention, Comparative example 3, 4 and 5 showed discoloration of silver.

  From the above results, it is clear that a cured product having good heat discoloration resistance and low gas permeability can be obtained by using the curable composition for encapsulating an optical semiconductor of the present invention, and such an optical semiconductor The curable composition for sealing was shown to be suitable as a sealing material for an optical semiconductor element.

  The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.

1 ... LED chip, 2 ... 1st lead frame,
2a: tip of first lead frame 2b: terminal of first lead frame,
2 '... recessed part, 3 ... 2nd lead frame, 3a ... tip part of 2nd lead frame,
3b: terminal portion of second lead frame, 4: bonding wire, 5: sealing material,
6 convex lens portion 7 translucent resin portion 8 package substrate 8 'concave portion
9: Electrode, 10, 10 ': Optical semiconductor device.

Claims (12)

(A) A straight chain having two or more alkenyl groups in one molecule, and further having a perfluoropolyether structure in the main chain and having an alkenyl group content of 0.0050 to 0.200 mol / 100 g Linear polyfluoro compound represented by the following general formula (3): 100 parts by mass

(Wherein R ⁵ and R ⁶ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and two or more are an alkenyl group. R ⁷ is independently of each other A hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, e and f each represents an integer of 1 to 150, and the average value of e + f is 2 to 300, and g is 1 to It is an integer of 6.)
(B) an organohydrogenpolysiloxane represented by the following general formula (1):

(Wherein, a is an integer of 1 to 50, b is an integer of 1 to 50, a + b is an integer of 2 to 100, and A is independently of each other a silicon atom, an oxygen atom or a nitrogen atom And a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain one or more of R ^{1 s} independently of ^one another is substituted or unsubstituted 1 And R ² is independently of each other a substituted or unsubstituted monovalent hydrocarbon group, and R ³ is independently of each other a substituted or unsubstituted monovalent hydrocarbon group. However, the order of bonding of-(SiO) (H) R ^2- and-(SiO) (A) R ^3- is not limited.)
(C) Platinum group metal based catalyst: 0.1 to 500 ppm in terms of platinum group metal atom,
(D) A monovalent perfluoroalkyl group bonded to a silicon atom via a hydrogen atom directly bonded to a silicon atom in one molecule, and a silicon atom, an oxygen atom or a divalent hydrocarbon group which may contain a nitrogen atom or Organopolysiloxanes having a monovalent perfluorooxyalkyl group and an epoxy group or trialkoxysilyl group or both bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom: 0.10 ~ 10.0 parts by mass,
(E) A monovalent unsaturated hydrocarbon group directly linked to a silicon atom, represented by the following general formula (2), and a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom Cyclic organopolysiloxane having a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom: 0.50 to 30.0 parts by mass

(Wherein, c is an integer of 1 to 4; d is an integer of 3 to 6; c + d is an integer of 4 to 10; R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group; D is an oxygen atom or a nitrogen atom Or a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain at least one substituent, and E is a monovalent unsaturated hydrocarbon group directly bonded to a silicon atom However, the order of bonding of-(SiO) (D) R ^4- and-(SiO) (E) R ^4- is not limited.)
The curable composition for optical semiconductor encapsulation according to claim 1, wherein the compounding amount of the component (B) is the alkenyl group of the component (A) and the monovalent unsaturated hydrocarbon group of the component (E). The amount of hydrogen atoms directly bonded to the silicon atoms contained in the component (B) is 0.50 to 2.0 moles relative to 1 mole in total, and the curable composition for encapsulating an optical semiconductor is cured. Transmittance of the light having a wavelength of 450 nm after leaving the obtained 2 mm thick cured product at 150 ° C. for 1,000 hours is 90.0% or more of the initial thickness, and the curable composition for encapsulating an optical semiconductor as described above The water vapor transmission rate of the 1-mm-thick hardened | cured material obtained by hardening | curing is 20.0 g / m < ² > * day or less, The curable composition for optical semiconductor sealing characterized by the above-mentioned. The linear polyfluoro compound represented by the general formula (3) is one or more straight chain selected from the group consisting of the following general formula (4), the following general formula (5) and the following general formula (6) It is a chain | strand-shaped polyfluoro compound, The curable composition for optical semiconductor sealing of Claim 1 characterized by the above-mentioned.

(Wherein R ⁷ is, independently of one another, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, e and f each represents an integer of 1 to 150, and the average value of e + f Is 2 to 300, g is an integer of 1 to 6, and R ⁸ is each independently a substituted or unsubstituted monovalent hydrocarbon group.)

(Wherein, R ⁷ , R ⁸ , e, f and g are as defined above)

(Wherein, R ⁷ , e, f and g are as defined above) Further, the curable composition for encapsulating an optical semiconductor according to claim 1 or 2, characterized in that it contains 0.010 to 5.0 parts by mass of a carboxylic acid anhydride as the component (F). object. The said (D) component is cyclic organopolysiloxane represented by following General formula (7), The hardening for optical semiconductor sealing of any one of the Claims 1-3 characterized by the above-mentioned. Sex composition.

(Wherein, h is an integer from 1 to 6, i is an integer from 1 to 4, j is an integer of 1 to 4, h + i + j is an integer of 4 to 10, ^{R 9,} independently from each other G is a monovalent hydrocarbon group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom independently of one another. Epoxy or trialkoxysilyl bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom independently of one another. a group or both, ^{however, -. (SiO) (H} ) R 9 -, - (SiO) (G) R 9 -, and ^{- (SiO) (J) R} 9 - is not limited binding order. )   The curable composition for optical semiconductor encapsulation according to claim 3, wherein the component (F) is a liquid at 23 ° C under normal pressure. The component (F) is a cyclic organopolysiloxane represented by the following general formula (8), and any one of claims 4 and 5 will be cited. The curable composition for optical semiconductor sealing as described in a term.

(Wherein k is an integer of 1 to 6; l is an integer of 1 to 4; m is an integer of 1 to 4; k + l + m is an integer of 4 to 10; R ¹⁰ independently of each other is a substituted or unsubstituted monovalent) And L independently represents a monovalent perfluoroalkyl group or monovalent valence bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And M is a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group independently of each other, provided that — (SiO) (H) R ¹⁰ -, - (SiO) (L ) R 10 - and ^{- (SiO) (M) R} 10 - is not limited binding order). The component (B), the component (D) and / or the (E) the definitive in Ingredient monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group, following general formula independently of one another (9) Or it is group represented by General formula (10), The curable composition for optical semiconductor sealing of any one of the Claims 1-4 characterized by the above-mentioned.
C _n F _{2n + 1-} (9)
(Wherein n is an integer of 1 to 10)

(In the formula, o is an integer of 1 to 10) The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in the component (F) which is a cyclic organopolysiloxane represented by the general formula (8) is, independently of each other, a group represented by the following general formula (9) It is group represented by General formula (10) or, The curable composition for optical semiconductor sealing of Claim 6 characterized by the above-mentioned.
C _n F _{2n + 1-} (9)
(Wherein n is an integer of 1 to 10)

(In the formula, o is an integer of 1 to 10) The initial transmittance of light having a wavelength of 450 nm of a 2 mm-thick cured product obtained by curing the curable composition for encapsulating an optical semiconductor is 85.0% or more. The curable composition for optical semiconductor sealing of any one of Claim 8 . The refractive index at 25 ° C., 589 nm (D line of sodium) of the cured product obtained by curing the curable composition for encapsulating an optical semiconductor is 1.30 or more and less than 1.40. for encapsulating an optical semiconductor curable composition according to any one of claims 9 to claim 1. An optical semiconductor device, and a cured product obtained by curing the curable composition for optical semiconductor encapsulation according to any one of claims 1 to 10 for encapsulating the optical semiconductor device. An optical semiconductor device characterized by having. The optical semiconductor device according to claim 11 , wherein the optical semiconductor element is a light emitting diode.

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