JP6329866B2 - Curable composition for sealing optical semiconductor and optical semiconductor device using the same - Google Patents

Description

  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 a perfluoropolyether structure in the main chain, directly bonded to a silicon atom in one molecule Properties such as heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, low temperature characteristics, etc. It has been proposed to obtain an excellent cured product with a good balance (Patent Document 1).

  And the composition which provided the self-adhesiveness with respect to a metal or a plastic base material by adding the organopolysiloxane which has a hydrosilyl group, an epoxy group, and / or trialkoxysilyl group to the above-mentioned composition is proposed. (Patent Document 2).

  Furthermore, a composition has been proposed in which adhesion to various substrates, particularly polyphenylene sulfide resin (PPS) and polyamide resin, is improved by adding a carboxylic acid anhydride to the above composition (Patent Document 3). ). Patent Document 4 proposes a composition capable of preventing a decrease in luminance even in the presence of a corrosive acidic gas or an alkaline gas.

  However, among the cured products obtained by curing the compositions actually prepared by these conventional techniques, those having a low type A durometer hardness of about 20 as defined in JIS K6253-3: 2012 are light-emitting diodes ( Hereinafter, when used as a sealing material of “LED”, the impact resistance as the sealing material may be insufficient. For example, when aligning an optical semiconductor device in which the LEDs are sealed with the above-described cured product in a certain direction and posture using a bowl-type vibrating parts feeder, the impact of the optical semiconductor devices colliding with the LED chip The problem that the bonding wire connecting the electrodes was often broken occurred.

  On the other hand, when the temperature cycle test was performed on the optical semiconductor device in which the LED was sealed with the cured product having a Type A durometer hardness of more than 90, cracks might occur in the cured product.

  Furthermore, in the optical semiconductor device in which the LED is sealed, the periphery of the LED may be plated with silver in order to increase the brightness. When the optical semiconductor device using the cured product obtained by curing the composition prepared by the above prior art as an LED encapsulant is used in an environment exposed to a sulfur-based gas, a sulfur-based gas is obtained over time. Often passes through the cured product and changes the color of silver to black, which often causes a problem of reduced brightness. Accordingly, there has been a demand for such a composition that exhibits lower gas permeability when cured into a cured product.

JP-A-8-199070 Japanese Patent Laid-Open No. 9-095615 JP 2001-072868 A JP 2009-277887 A

  The present invention has been made in view of the above circumstances, and is a curable composition for encapsulating optical semiconductors that provides a cured product having excellent impact resistance and crack resistance and low gas permeability, and the optical semiconductor encapsulating It aims at providing the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material obtained by hardening | curing a curable composition.

（式中、ａは３〜１０の整数であり、Ａはパーフルオロアルキレン基、パーフルオロオキシアルキレン基、又はその両方を含む２価の有機基であり、Ｄ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置換又は非置換の２価の炭化水素基であり、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は互いに独立して水素原子、又は、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^２のうちの三つ以上は水素原子である。）
（Ｃ）白金族金属系触媒：白金族金属原子換算で０．１〜５００ｐｐｍ、
（Ｄ）下記一般式（２）で表される環状オルガノポリシロキサン：０．１０〜１０．０質量部、

（式中、ｂは１〜６の整数であり、ｃは１〜４の整数であり、ｄは１〜４の整数であり、ｂ＋ｃ＋ｄは４〜１０の整数であり、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り、Ｅ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、Ｇ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又はトリアルコキシシリル基もしくはその両方である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^３−、−（ＳｉＯ）（Ｅ）Ｒ^３−、及び−（ＳｉＯ）（Ｇ）Ｒ^３−の結合の順番は限定されない。）
（Ｅ）カルボン酸無水物：０．０１０〜１０．０質量部
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、該組成物中に含まれるアルケニル基１モルに対して、前記（Ｂ）成分中の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、該光半導体封止用硬化性組成物を硬化して得られる硬化物の硬さが、ＪＩＳ Ｋ６２５３−３：２０１２に規定されるタイプＡデュロメータで３０〜９０の値となる光半導体封止用硬化性組成物を提供する。 In order to solve the above problems, the present invention provides:
(A) A straight chain 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 -Like polyfluoro compound: 100 parts by mass,
(B) an organohydrogenpolysiloxane represented by the following general formula (1),

(Wherein, a is an integer of 3 to 10, A is a divalent organic group containing a perfluoroalkylene group, a perfluorooxyalkylene group, or both, D is independently of each other a silicon atom, A substituted or unsubstituted divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom; R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other; and R ² is independently of each other. A hydrogen atom, or a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And three or more of R ² are hydrogen atoms.)
(C) Platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom,
(D) Cyclic organopolysiloxane represented by the following general formula (2): 0.10 to 10.0 parts by mass,

(In the formula, b is an integer of 1 to 6, c is an integer of 1 to 4, d is an integer of 1 to 4, b + c + d is an integer of 4 to 10, and R ³ are independent of each other. Substituted or unsubstituted monovalent hydrocarbon group, and E is independently monovalent bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. An epoxy group or trialkoxysilyl bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom, independently of each other, and G is a perfluoroalkyl group or a monovalent perfluorooxyalkyl group However, the order of bonding of — (SiO) (H) R ³ —, — (SiO) (E) R ³ —, and — (SiO) (G) R ³ — is not limited. )
(E) Carboxylic anhydride: a curable composition for sealing an optical semiconductor containing 0.010 to 10.0 parts by mass, wherein the blending amount of the component (B) is included in the composition. The amount of hydrogen atoms directly bonded to the silicon atom in the component (B) is 0.50 to 2.0 mol with respect to 1 mol of the alkenyl group, and the curable composition for optical semiconductor encapsulation is cured. The curable composition for optical semiconductor sealing by which the hardness of the hardened | cured material obtained by this becomes a value of 30-90 with the type A durometer prescribed | regulated to JISK6253-3: 2012 is provided.

  In such a curable composition for encapsulating an optical semiconductor, which is an addition-curable fluoropolyether-based curable composition containing all the components (A) to (E) and having a hardness of the cured product within the above range. If it exists, the cured | curing material which is excellent in impact resistance and crack resistance, and has further low gas permeability can be obtained.

（式中、ｅは１〜４の整数であり、ｆは３〜６の整数であり、ｅ＋ｆは４〜１０の整数であり、Ｒ^４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、Ｊ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、Ｌは互いに独立してケイ素原子に直結したアルケニル基である。ただし、−（ＳｉＯ）（Ｊ）Ｒ^４−及び−（ＳｉＯ）（Ｌ）Ｒ^４−の結合の順番は限定されない。） Furthermore, it is preferable to contain 0.10-50.0 mass parts of cyclic organopolysiloxane represented by following General formula (3) as (F) component.

(In the formula, e is an integer of 1 to 4, f is an integer of 3 to 6, e + f is an integer of 4 to 10, and R ⁴ is independently a substituted or unsubstituted monovalent carbonization. Each independently represents a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to the silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. A fluorooxyalkyl group, and L is an alkenyl group directly bonded to a silicon atom independently of each other, provided that the bonding order of — (SiO) (J) R ⁴ — and — (SiO) (L) R ⁴ — Is not limited.)

  If it is the curable composition for optical semiconductor sealing containing the said (A) component-(E) component, and also the said (F) component as needed, it is excellent in impact resistance and crack resistance, and is low. A cured product having gas permeability can be obtained. Therefore, the hardened | cured material of the said curable composition for optical semiconductor sealing can be used suitably for the sealing material of an optical semiconductor element, especially the sealing material for protecting LED.

（式中、Ｒ^６及びＲ^７は互いに独立して、アルケニル基、又は、置換又は非置換の１価の炭化水素基であり、一つ以上はアルケニル基である。Ｒ^８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、ｇ及びｈはそれぞれ１〜１５０の整数であって、且つｇ＋ｈの平均値は２〜３００であり、ｉ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 (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 are alkenyl groups. R ⁸ is independently , A hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group, g and h are each an integer of 1 to 150, an average value of g + h is 2 to 300, and i is 0 to 0 (It is an integer of 6.)

（式中、Ｒ^８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、ｇ及びｈはそれぞれ１〜１５０の整数であって、且つｇ＋ｈの平均値は２〜３００であり、ｉは０〜６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る。）

（式中、Ｒ^８、Ｒ^９、ｇ、ｈ、及びｉは上記と同じである。）

（式中、Ｒ^８、ｇ、ｈ、及びｉ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 (5), the following general formula (6), and the following general formula (7). Is preferred.

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

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

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

  With such a component (A), the properties such as heat resistance, chemical resistance, solvent resistance, mold release, water repellency, oil repellency, and low temperature characteristics are well balanced, and curing is more excellent as a sealing material. You can get things.

Moreover, it is preferable that the perfluorooxyalkylene group contained in A of the said (B) component is a group containing 1-500 repeating units represented by following General formula (8).
-C _{e '} F _2e' O- (8)
(Wherein e ′ is an integer of 1 to 6 independently for each unit)

（式中、Ｒ^１０は互いに独立にフッ素原子又はＣＦ_３基であり、ｊは１〜４の整数であり、ｋ及びｎはそれぞれ０〜２００の整数であり、ｋ＋ｎの平均値は０〜４００であり、ｌは２〜６の整数である。また、各繰り返し単位の結合の順番は限定されない。）

（式中、ｐは１〜２００の整数であり、ｊは上記と同じである。）

（式中、Ｒ^１０、ｊ、ｋ、及びｎは上記と同じである。また、各繰り返し単位の結合の順番は限定されない。） Furthermore, it is preferable that A of the component (B) is a group selected from the group consisting of the following general formula (9), the following general formula (10), and the following general formula (11).

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

(In the formula, p is an integer of 1 to 200, and j is the same as above.)

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

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

（式中、ｑは１〜６の整数、ｒは１〜４の整数、ｓは１〜４の整数、ｑ＋ｒ＋ｓは４〜１０の整数、Ｒ^１１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、Ｍ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、Ｑ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^１１−、−（ＳｉＯ）（Ｍ）Ｒ^１１−及び−（ＳｉＯ）（Ｑ）Ｒ^１１−の結合の順番は限定されない。）

（式中、Ｒ^１１、Ｍ、及びＱは上記と同じであり、ｔは１〜３の整数、ｕは０〜２の整数、ｔ＋ｕは３である。） The component (E) is preferably a carboxylic acid anhydride selected from the group consisting of the following general formula (12) and the following general formula (13).

(In the formula, q is an integer of 1 to 6, r is an integer of 1 to 4, s is an integer of 1 to 4, q + r + s is an integer of 4 to 10, and R ¹¹ is independently a substituted or unsubstituted monovalent group. M 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, or a monovalent group, independently of each other And Q is a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group independently of each other, provided that — (SiO) (H) R ^11. The order of bonding of —, — (SiO) (M) R ¹¹ — and — (SiO) (Q) R ¹¹ — is not limited.)

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

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

（式中、ｗは１〜１０の整数である） The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group is preferably a group represented by the following general formula (14) or general formula (15) independently of each other.
C _v F _{2v + 1} − (14)
(In the formula, v is an integer of 1 to 10.)

(Wherein w is an integer of 1 to 10)

  If it is such a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, a composition having better compatibility with the component (A), dispersibility, and uniformity after curing can be obtained. it can.

Moreover, it is preferable that the water vapor transmission rate of 1 mm thick hardened | cured material obtained by hardening | curing the said curable composition for optical semiconductor sealing is 15.0 g / m < ² > * day or less.

Thus, when the water vapor transmission rate is 15.0 g / m ² · day or less, in the optical semiconductor device in which the periphery of the LED is plated with silver, a cured product obtained by curing the composition of the present invention is used. When used as a sealing material for LEDs, it is preferable that silver is blackened by the gas and the brightness is not lowered even when exposed to a sulfur-based gas.

  Furthermore, it is preferable that the viscosity at 23 degreeC prescribed | regulated to JISK7117-1: 1999 of the said curable composition for optical semiconductor sealing is 50.0-50,000 mPa * s.

  Thus, if the viscosity is 50.0 mPa · s or more, the fluidity is too high and there is no fear that it becomes difficult to control the dispenser that pots a certain amount in the LED package, and it is preferable that the viscosity is 50,000 mPa · s or less. If it exists, it takes time to level after the curable composition for encapsulating the optical semiconductor is potted in the LED package, and there is no possibility that the productivity is lowered, which is preferable.

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

  As described above, when the refractive index is 1.30 or more and less than 1.40, the light is emitted from the LED in the optical semiconductor device in which the LED is sealed with the cured product obtained by curing the composition of the present invention. This is preferable because the efficiency with which light can be extracted to the outside is not likely to be insufficient.

  Moreover, this invention provides the optical semiconductor device which has an optical semiconductor element and the hardened | cured material obtained by hardening | curing the said curable composition for optical semiconductor sealing for sealing this optical semiconductor element.

  The curable composition for encapsulating an optical semiconductor of the present invention is excellent in impact resistance and crack resistance, and can provide a cured product having lower gas permeability. In the optical semiconductor device thus manufactured, even if the optical semiconductor devices collide with each other, damage to members is less likely to occur, so that yield and productivity can be improved. In addition, even if a temperature cycle test is performed, cracks are hardly generated in the cured product, so that reliability can be improved. Furthermore, since it becomes difficult for sulfur-type gas to permeate | transmit a hardened | cured material, the fall of brightness can be suppressed.

  The optical semiconductor element is preferably a light emitting diode.

  Thus, the hardened | cured material of the curable composition for optical semiconductor sealing of this invention can be used suitably especially as a sealing material for protecting a light emitting diode.

  The curable composition for sealing an optical semiconductor of the present invention is a combination of the above components (A) to (E), and further, if necessary, the component (F), whereby the cured product has good impact resistance and crack resistance, Furthermore, since it has low gas permeability, the optical semiconductor device in which the optical semiconductor element is sealed with the cured product can be manufactured without damaging the member such as disconnection of the bonding wire. Moreover, even if it performs a temperature cycle test, generation | occurrence | production of the crack of hardened | cured material is suppressed. Further, even if the optical semiconductor device is used in an environment exposed to sulfur-based gas, it is possible to suppress a decrease in brightness, which makes it 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, an optical semiconductor element is sealed with a curable composition for optical semiconductor encapsulation having good impact resistance and crack resistance, and further low gas permeability, and a cured product obtained by curing the composition. There is a need for a stopped optical semiconductor device.

As a result of intensive investigations to achieve the above object, the inventors of the present invention have good impact resistance if the composition contains the following components (A) to (E) and, if necessary, the component (F). The present invention has been completed by finding that the present invention provides a curable composition for encapsulating optical semiconductors that gives a cured product having good properties and crack resistance and low gas permeability.
Hereinafter, the present invention will be described in detail. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[(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 that is / 100 g.

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

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

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

  In the general 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 an integer of 1 to 80. More preferably, it is an integer of 1-50, and the average value of c ′ + d ′ is preferably 2-380, more preferably 2-250.

  The alkenyl group content contained 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 cross-linking is insufficient and a curing failure occurs. When the alkenyl group content exceeds 0.200 mol / 100 g, the rubber elastic body of this cured product As a result, the mechanical properties of the

（式中、Ｒ^６及びＲ^７は互いに独立して、アルケニル基、又は、置換又は非置換の１価の炭化水素基であり、一つ以上はアルケニル基である。Ｒ^８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、ｇ及びｈはそれぞれ１〜１５０の整数であって、且つｇ＋ｈの平均値は２〜３００であり、ｉは０〜６の整数である。） (A) As a preferable example of a component, the linear polyfluoro compound represented by following General formula (4) is mentioned.

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

Here, examples of the alkenyl group contained in R ⁶ and R ⁷ include the same alkenyl groups as described above, and other substituted or unsubstituted monovalent hydrocarbon groups preferably have 1 to 12 carbon atoms. In particular, those having 1 to 10 carbon atoms are preferred. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; aryl groups such as phenyl group and tolyl group Groups; aralkyl groups such as a benzyl group and a phenylethyl group; and monovalent hydrocarbon groups obtained by substituting part or all of the hydrogen atoms of these groups with halogen atoms such as fluorine. Of these, a methyl group and an ethyl group are particularly preferable.

Examples of the substituted or unsubstituted monovalent hydrocarbon group contained in R ⁸ include the same groups as those exemplified above for the substituted or unsubstituted monovalent hydrocarbon group of R ⁶ and R ⁷ .

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

  More preferred examples of the component (A) include linear polyfluoro compounds represented by the following general formulas (5) to (7).

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

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

（式中、ｇ及びｈは上記と同様である。）

(Wherein g and h are the same as above)

（式中、ｇ及びｈは上記と同様である。） Specific examples of the linear polyfluoro compound represented by the general formula (6) include those represented by the following formula.

(Wherein g and h are the same as above)

（式中、ｇ及びｈは上記と同じである。） Furthermore, what is represented by a following formula is mentioned as a specific example of the linear polyfluoro compound represented by the said General formula (7).

(Wherein g and h are the same as above)

  The viscosity of the component (A) at 23 ° C. is preferably from 500 to 100,000 mPa · s, more preferably from 1,000 to 50,000 mPa · s, as measured by the viscosity specified in JIS K7117-1: 1999. It is desirable to use the composition of the present invention as an LED encapsulant.

  The linear polyfluoro compound of the said (A) component can be used individually by 1 type or in combination of 2 or more types. That is, in the linear polyfluoro compound represented by the general formulas (5) to (7), one kind may be used alone, or two or more kinds may be used in combination.

（式中、ａは３〜１０の整数であり、Ａはパーフルオロアルキレン基、パーフルオロオキシアルキレン基、又はその両方を含む２価の有機基であり、Ｄ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置換又は非置換の２価の炭化水素基であり、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は互いに独立して水素原子、又は、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^２のうちの三つ以上は水素原子である。） [Component (B)]
The component (B) is an organohydrogenpolysiloxane represented by the following general formula (1) and functions as a crosslinking agent for the component (A). Moreover, this (B) component contributes to the low gas permeability of the hardened | cured material obtained by hardening | curing the composition of this invention.

(Wherein, a is an integer of 3 to 10, A is a divalent organic group containing a perfluoroalkylene group, a perfluorooxyalkylene group, or both, D is independently of each other a silicon atom, A substituted or unsubstituted divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom; R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other; and R ² is independently of each other. A hydrogen atom, or a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And three or more of R ² are hydrogen atoms.)

  In the said General formula (1), a is an integer of 3-10, Preferably it is an integer of 3-6.

A is a divalent organic group containing a perfluoroalkylene group, a perfluorooxyalkylene group, or both. Such a perfluoroalkylene group is represented by the following general formula (8 ′). Groups.
_{-C m F 2m - (8 '} )
(In the formula, m is preferably an integer of 1 to 10, more preferably an integer of 1 to 5.)

On the other hand, as the perfluorooxyalkylene group, the following general formula (8):
-C _{e '} F _2e' O- (8)
(Wherein e ′ is an integer of 1 to 6 independently for each unit)
1 to 500, more preferably 2 to 300, and even more preferably 5 to 200 repeating units represented by

  E 'may be different for each repeating unit, and is an integer of 1 to 6, preferably an integer of 1 to 4.

As a specific example of the repeating unit represented by the general formula (8),
-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-,
Etc. The perfluorooxyalkylene group may be composed of one of these repeating units, or a combination of two or more.

（式中、Ｒ^１０は互いに独立にフッ素原子又はＣＦ_３基であり、ｊは１〜４の整数であり、ｋ及びｎはそれぞれ０〜２００の整数であり、ｋ＋ｎの平均値は０〜４００であり、ｌは２〜６の整数である。また、各繰り返し単位の結合の順番は限定されない。）

（式中、ｐは１〜２００の整数であり、ｊは上記と同じである。）

（式中、Ｒ^１０、ｊ、ｋ、及びｎは上記と同じである。また、各繰り返し単位の結合の順番は限定されない。） A composed of the perfluoroalkylene group represented by the general formula (8 ′) and the perfluorooxyalkylene group represented by the general formula (8) is represented by the following general formulas (9) to (11). Are preferred.

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

(In the formula, p is an integer of 1 to 200, and j is the same as above.)

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

In the general 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 1 to 150, the average value of k + n is 0 to 400, preferably 2 to 300, and l is an integer of 2 to 6, preferably 2 to 5. However, the order of bonding of each repeating unit in the general formula (9) is not limited.

In the said General formula (10), p is an integer of 1-200, Preferably it is an integer of 1-150, j is the same as the above.

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

  Next, in the general formula (1), D is independently a substituted or unsubstituted divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom, specifically, An alkylene group having 2 to 12 carbon atoms, a group in which some or all of the hydrogen atoms of the alkylene group are substituted with halogen atoms such as fluorine, or an ether bond, an ester bond, an amide bond, and a divalent group. And those having an aromatic hydrocarbon group or the like interposed therebetween. Specific examples include the groups shown below. In the following groups, it is preferable that the left side is bonded to A and the right side is bonded to a silicon atom.

In the general formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other, and the substituted or unsubstituted monovalent groups of R ⁶ , R ⁷ , and R ⁸ described above. Examples of the hydrocarbon group are the same as those exemplified above.

Further, in the general formula (1), R ^{2 s} are monovalent bonded to a silicon atom through a hydrogen atom or 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, and at least three of R ^{2 in} the formula are hydrogen atoms.

（式中、ｗは１〜１０の整数、好ましくは２〜８の整数である。） Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include groups represented by the following general formulas (14) and (15).
C _v F _{2v + 1} − (14)
(In the formula, v is an integer of 1 to 10, preferably an integer of 3 to 7.)

(In the formula, w is an integer of 1 to 10, preferably an integer of 2 to 8.)

In addition, the divalent hydrocarbon group that includes the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group and the silicon atom and may contain a silicon atom, an oxygen atom, or a nitrogen atom has 2 carbon atoms. To 12 alkylene groups, or those having an ether bond, silicon atom, amide bond, divalent aromatic hydrocarbon group, carbonyl bond or the like interposed in the group, specifically the groups shown below: It can be illustrated.

  Examples of such component (B) include compounds represented by the following general formula. In the formula, k and n are the same as described above.

  This (B) component may be used individually by 1 type, and may use 2 or more types together. The blending amount of the component (B) is such that the hydrogen atom (SiH group) directly connected to the silicon atom in the component (B) is 0.50 to 1 mol of the alkenyl group contained in the composition of the present invention. The amount is 2.0 mol, more preferably 0.70 to 1.6 mol. If the SiH group is less than 0.50 mol, the degree of crosslinking becomes insufficient, while if it exceeds 2.0 mol, the storage stability may be impaired or the physical properties of the cured product obtained after curing may be deteriorated. There is.

[Component (C)]
The platinum group metal catalyst which is the component (C) of the present invention is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst contains an alkenyl group contained in the composition, in particular, an alkenyl group in component (A) and an alkenyl group in component (F), an SiH group contained in the composition, and component (B). It is a catalyst that promotes the addition reaction with SiH groups therein. This hydrosilylation reaction catalyst is generally a noble metal or a compound thereof and is expensive, and thus platinum or platinum compounds that are relatively easily available are 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 its compounds. For example, 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 formula, Ph represents a phenyl group.

  When these catalysts are used, they can be used in a solid state when they are solid catalysts, but in order to obtain a more uniform cured product, chloroplatinic acid or a complex such as toluene or ethanol is used. It is preferable to use what was melt | dissolved in the appropriate solvent of (A), making it compatible with the linear polyfluoro compound of (A) component.

  (C) The compounding quantity of component is an effective amount as a hydrosilylation reaction catalyst, 0.1-500 ppm with respect to 100 mass parts of (A) component, Most preferably, 0.5-200 ppm (platinum group metal atom) Mass conversion), but can be appropriately increased or decreased depending on the desired curing rate.

（式中、ｂは１〜６の整数であり、ｃは１〜４の整数であり、ｄは１〜４の整数であり、ｂ＋ｃ＋ｄは４〜１０の整数であり、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り、Ｅ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、Ｇ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又はトリアルコキシシリル基もしくはその両方である。ただし、−（ＳｉＯ）（Ｈ）Ｒ^３−、−（ＳｉＯ）（Ｅ）Ｒ^３−、及び−（ＳｉＯ）（Ｇ）Ｒ^３−の結合の順番は限定されない。） [(D) component]
The component (D) of the present invention is a cyclic organopolysiloxane represented by the following general formula (2), and functions as an adhesive agent that gives self-adhesion to a cured product obtained by curing the composition of the present invention. Have

(In the formula, b is an integer of 1 to 6, c is an integer of 1 to 4, d is an integer of 1 to 4, b + c + d is an integer of 4 to 10, and R ³ are independent of each other. Substituted or unsubstituted monovalent hydrocarbon group, and E is independently monovalent bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. An epoxy group or trialkoxysilyl bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom, independently of each other, and G is a perfluoroalkyl group or a monovalent perfluorooxyalkyl group However, the order of bonding of — (SiO) (H) R ³ —, — (SiO) (E) R ³ —, and — (SiO) (G) R ³ — is not limited. )

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

R ³ is independently a substituted or unsubstituted monovalent hydrocarbon group, and the above-described substituted or unsubstituted monovalent hydrocarbon group of R ¹ , R ⁶ , R ⁷ , and R ⁸ The same groups as exemplified can be mentioned.

Furthermore, E is independently of each other a monovalent perfluoroalkyl group or a 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. Examples thereof include the same groups as the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group used for R ² described above. This E is a group introduced as appropriate from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

G is independently an epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom. As such an epoxy group, what is represented by the following general formula (18) is mentioned, for example.

In the general formula (18), R ¹² may contain an oxygen atom, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Group, ethylene group, propylene group, butylene group, hexylene group, octylene group and other alkylene groups, cyclohexylene group and other cycloalkylene groups, oxyethylene group, oxypropylene group, oxybutylene group and other oxyalkylene groups It is done.

Specific examples of such an epoxy group include those shown below.

On the other hand, examples of the trialkoxysilyl group include those represented by the following general formula (19).

In the general formula (19), R ¹³ is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and specifically includes a methylene group, an ethylene group, a propylene group, or butylene. And alkylene groups such as a hexylene group, a cyclohexylene group, and an octylene group. R ¹⁴ is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples thereof include alkyl groups such as a methyl group, an ethyl group, and an n-propyl group. Can be mentioned.

Specific examples of such trialkoxysilyl groups include those shown below.

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

  This (D) component may be used individually by 1 type, and may use 2 or more types together. Moreover, the usage-amount of (D) component is 0.10-10.0 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 0.50-8.0 mass parts. When the amount is less than 0.10 parts by mass, sufficient adhesiveness cannot be obtained. When the amount exceeds 10.0 parts by mass, the fluidity of the composition is deteriorated, and the cured product obtained by curing the composition of the present invention. The physical strength of the material may be reduced.

[(E) component]
The component (E) of the present invention is a carboxylic acid anhydride, improves the adhesion imparting ability of the component (D), and promotes the self-adhesive expression of the cured product obtained by curing the composition of the present invention. Is for. As this (E) component, what is used as a hardening | curing agent for epoxy resins can be used.

（式中、ｑは１〜６の整数、ｒは１〜４の整数、ｓは１〜４の整数、ｑ＋ｒ＋ｓは４〜１０の整数、Ｒ^１１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、Ｍ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、Ｑ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^１１−、−（ＳｉＯ）（Ｍ）Ｒ^１１−及び−（ＳｉＯ）（Ｑ）Ｒ^１１−の結合の順番は限定されない。）

（式中、Ｒ^１１、Ｍ、及びＱは上記と同じであり、ｔは１〜３の整数、ｕは０〜２の整数、ｔ＋ｕは３である。） As such (E) component, the carboxylic acid anhydride represented by the following general formula (12) or the following general formula (13) is preferable.

(In the formula, q is an integer of 1 to 6, r is an integer of 1 to 4, s is an integer of 1 to 4, q + r + s is an integer of 4 to 10, and R ¹¹ is independently a substituted or unsubstituted monovalent group. M 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, or a monovalent group, independently of each other And Q is a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group independently of each other, provided that — (SiO) (H) R ^11. The order of bonding of —, — (SiO) (M) R ¹¹ — and — (SiO) (Q) R ¹¹ — is not limited.)

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

In the general 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 The integer of 1-3, the sum of q, r, and s is an integer of 4-10, Preferably it is an integer of 4-8. However, the order of bonding of — (SiO) (H) R ¹¹ —, — (SiO) (M) R ¹¹ —, and — (SiO) (Q) R ¹¹ — is not limited.

R ¹¹ is independently a substituted or unsubstituted monovalent hydrocarbon group, and the substituted or unsubstituted monovalent carbon of R ¹ , R ³ , R ⁶ , R ⁷ , and R ⁸ described above. Examples thereof are the same as those exemplified for the hydrogen group.

Further, M is independently of each other a monovalent perfluoroalkyl group or a 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 monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group used for R ² and E described above. This M is a group introduced as appropriate from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

Q is independently of each other a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, and specifically includes a group represented by the following general formula (20). .

In the general formula (20), R ¹⁵ is preferably a divalent hydrocarbon group having 1 to 15 carbon atoms, and specifically includes a methylene group, an ethylene group, a propylene group, a butylene group, and the like. Or a propylene group is especially preferable.

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

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

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

This (E) component may be used individually by 1 type, and may use 2 or more types together.
The 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 with respect to 100 parts by mass of the component (A). When the amount is less than 0.010 parts by mass, it is not possible to obtain a sufficient effect for promoting the adhesive expression of the composition of the present invention. When the amount exceeds 10.0 parts by mass, the fluidity of the composition is increased. There is a risk that it will deteriorate and the storage stability of the composition will be impaired.

（式中、ｅは１〜４の整数であり、ｆは３〜６の整数であり、ｅ＋ｆは４〜１０の整数であり、Ｒ^４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、Ｊ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、Ｌは互いに独立してケイ素原子に直結したアルケニル基である。ただし、−（ＳｉＯ）（Ｊ）Ｒ^４−及び−（ＳｉＯ）（Ｌ）Ｒ^４−の結合の順番は限定されない。） The curable composition for sealing an optical semiconductor of the present invention preferably contains the following component (F) as an optional component.
[(F) component]
As the component (F) of the present invention, a cyclic organopolysiloxane represented by the following general formula (3) is preferably used, and the cured product obtained by curing the composition of the present invention has even better impact resistance. It imparts sex.

(In the formula, e is an integer of 1 to 4, f is an integer of 3 to 6, e + f is an integer of 4 to 10, and R ⁴ is independently a substituted or unsubstituted monovalent carbonization. Each independently represents a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to the silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. A fluorooxyalkyl group, and L is an alkenyl group directly bonded to a silicon atom independently of each other, provided that the bonding order of — (SiO) (J) R ⁴ — and — (SiO) (L) R ⁴ — Is not limited.)

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

R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group, and the above-described substituted or unsubstituted monovalent hydrocarbon of R ¹ , R ³ , R ⁶ , R ⁷ , R ⁸ , and R ¹¹ The same group as the example of group is mentioned.

Further, J is 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 independently of each other. And a group similar to the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group used for R ² , E, and M described above. This J is a group introduced as appropriate from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

  L is an alkenyl group directly bonded to a silicon atom, and specific examples include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and a decenyl group. Among these, a vinyl group or an allyl group is particularly preferable.

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

この（Ｆ）成分は、１種単独で使用してもよいし、２種以上のものを併用してもよい。また、（Ｆ）成分を含む場合の使用量は、（Ａ）成分１００質量部に対して０．１０〜５０．０質量部が好ましく、より好ましくは１．０〜４０．０質量部の範囲である。０．１０質量部以上の場合、本発明の組成物を硬化して得られる硬化物に適度な耐衝撃性を付与する効果が十分となり、５０．０質量部以下の場合、本発明の組成物を硬化して得られる硬化物の耐クラック性又は低いガス透過性を損なう恐れがない。

This (F) component may be used individually by 1 type, and may use 2 or more types together. In addition, the amount used when the component (F) is included is preferably 0.10 to 50.0 parts by mass, more preferably 1.0 to 40.0 parts by mass with respect to 100 parts by mass of the component (A). It is. In the case of 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 in the case of 50.0 parts by mass or less, the composition of the present invention. There is no fear of impairing the crack resistance or low gas permeability of the cured product obtained by curing.

[Other ingredients]
In the curable composition for sealing an optical semiconductor of the present invention, in addition to the components (A) to (E) and (F) described above, a plasticizer, a viscosity modifier, Various compounding agents such as an adhesion promoter other than the flexibility imparting agent, the inorganic filler, the reaction control agent, and the component (E) can be added as necessary. The compounding quantity of these additives is arbitrary.

As a plasticizer, a viscosity modifier, and a flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (21) and / or a linear poly represented by the following general formulas (22) and (23) A fluoro compound can be used in combination.
_{Rf- (T) f '-CH =} CH 2 (21)
[Wherein Rf is a group represented by the following general formula (24);
_{F- [CF (CF 3) CF} 2 O] g '-C h' F 2h '- (24)
(In the formula, g ′ is preferably an integer of 1 to 200, more preferably an integer of 1 to 150, and h ′ is preferably an integer of 1 to 3).
T is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ¹⁶ —X— (where 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)
(In the formula, X ′ is a group represented by C _{j ′} F _{2j ′ + 1} − (j ′ is 1 to 3), and i ′ is preferably an integer of 1 to 200, more preferably an integer of 2 to 100. .)
_{X'-O- (CF 2 O)} k '(CF 2 CF 2 O) l' -X '(23)
(Wherein X ′ is the same as above, k ′ and l ′ are each preferably an integer of 1 to 200, more preferably an integer of 1 to 100, and an average value of k ′ + l ′ is preferred. Is 2 to 400, more preferably 2 to 300.)

  Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (21) include the following. In the following formulae, Me represents a methyl group.

（ここで、ｍ’＝１〜１００である。）

(Here, m ′ = 1 to 100.)

Specific examples of the linear polyfluoro compound represented by the general 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
(Here, n ′, o ′ and p ′ are each preferably an integer of 1 to 200, more preferably an integer of 1 to 150, and the average value of o ′ + p ′ is preferably an integer of 2 to 400, Preferably it is an integer of 2 to 300.)

  Further, the viscosity (23 ° C.) of the polyfluoro compound represented by the general formulas (21) to (23) is 5.00 to 100,000 mPa · s, particularly 50, in the same measurement method as that for the component (A). It is desirable to be in the range of 0.0 to 50,000 mPa · s.

  Examples of inorganic fillers include silica powder such as fumed silica, precipitated silica, spherical silica, silica airgel, or the like, or the surface of the silica powder is treated with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, etc. The silica powder, and further, the surface-treated silica powder has a monovalent perfluoroalkyl group represented by the general formula (14) or a monovalent perfluorooxyalkyl group represented by the general formula (15). Silica-based reinforcing filler such as silica powder re-treated with organosilane or organosiloxane, quartz powder, fused silica powder, diatomaceous earth, reinforcing filler such as calcium carbonate, semi-reinforcing filler, titanium oxide, iron oxide, Carbon black, inorganic pigments such as cobalt aluminate, titanium oxide, iron oxide, carbon black, cerium oxide Heat resistance improver such as cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate, thermal conductivity imparting agent such as alumina, boron nitride, silicon carbide, metal powder, conductivity such as carbon black, silver powder, conductive zinc white Examples include an imparting agent. In addition, magnesium fluoride, aluminum fluoride, calcium fluoride, lithium fluoride, sodium fluoride, thorium silicon oxide, and other inorganic materials having a refractive index of 1.50 or less at 25 ° C. and 589 nm (sodium D-line) Fine particles are also useful as reinforcing fillers.

  Examples of the control agent for the hydrosilylation reaction catalyst include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl. An acetylenic alcohol such as -1-pentyn-3-ol and phenylbutynol, and a chlorosilane having a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group similar to G described above and an acetylenic alcohol Examples include reactants, 3-methyl-3-penten-1-in, 3,5-dimethyl-3-hexen-1-in, triallyl isocyanurate, polyvinyl siloxane, organophosphorus compounds, and the like. Curing reactivity and storage stability can be kept moderate.

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

  The manufacturing method in particular of the curable composition for optical semiconductor sealing of this invention is not restrict | limited, It can manufacture by knead | mixing said (A)-(E) component, (F) component, and another arbitrary component. . At that time, if necessary, a mixing apparatus such as a planetary mixer, a loss mixer, and a Hobart mixer, and a kneading apparatus such as a kneader and a three-roll can be used.

  Regarding the constitution of the curable composition for encapsulating an optical semiconductor of the present invention, the above-described components (A) to (E), the component (F) and other optional components are all handled as one composition depending on the use. You may comprise as 1 liquid type, or you may make it 2 liquid type and mix both 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 impact resistance and crack resistance, and further low gas permeability. It is useful as a sealing material for protecting optical semiconductor elements such as organic EL. Although the hardening temperature in particular of this curable composition for optical semiconductor sealing is not restrict | limited, Usually, 20-250 degreeC, Preferably, it is 40-200 degreeC. In addition, the curing time in that case may be appropriately selected as long as the crosslinking reaction and the adhesion reaction with various semiconductor package materials are completed. In general, 10 minutes to 10 hours are preferable, and 30 minutes to 8 hours are more preferable. preferable.

  The hardened | cured material obtained by hardening | curing the composition of this invention has the type A durometer hardness prescribed | regulated to JISK6253-3-3: 2012 30-90, Preferably it is 35-85. If it is less than 30, the impact resistance as an LED sealing material may be inferior. On the other hand, if it is higher than 90, the LED sealing material may be inferior in crack resistance.

Further, the water vapor permeability of a 1 mm thick cured product obtained by curing the composition of the present invention is preferably 15.0 g / m ² · day or less, more preferably 13.0 g / m ² · day or less. It is. If it is 15.0 g / m ² · day or less, a cured product obtained by curing the composition of the present invention is used as an LED sealing material in an optical semiconductor device in which the periphery of the LED is plated with silver Even if it is exposed to sulfur-based gas, it is preferable because silver is not blackened by the gas and the brightness is not lowered. The water vapor transmission rate is a value measured using a L80-5000 type water vapor transmission meter manufactured by Lyssy in accordance with JIS K7129: 2008.

  Furthermore, the viscosity of the composition of the present invention at 23 ° C. defined in JIS K7117-1: 1999 is preferably 50.0 to 50,000 mPa · s, and preferably 100 to 30,000 mPa · s from the viewpoint of handling workability. Is more preferable. If it is 50.0 mPa · s or more, the fluidity is too high, and it is preferable that it is difficult to control a dispenser that pots a certain amount in the LED package, and if it is 50,000 mPa · s or less, the composition This is preferable because there is no fear that productivity takes a long time to level after the LED is potted in the LED package.

  Moreover, it is preferable that the refractive index in 25 degreeC and 589 nm (D line of sodium) of the hardened | cured material obtained by hardening | curing the composition of this invention is 1.30 or more and less than 1.40. When the refractive index is within this range, in an optical semiconductor device in which the optical semiconductor element is sealed with a cured product obtained by curing the composition of the present invention, light emitted from the LED can be extracted to the outside. The efficiency is preferable because there is no fear that the efficiency is lowered by the design of the optical semiconductor device.

  In using the composition of the present invention, the composition may be selected from suitable fluorine-based solvents such as 1,3-bis (trifluoromethyl) benzene, fluorinate (manufactured by 3M), par. 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 a curable composition for encapsulating an optical semiconductor containing the above components (A) to (E), (F) and other optional components and having the above-mentioned properties, impact resistance and crack resistance A cured product having excellent properties and low gas permeability can be obtained.

  The structure of the optical semiconductor device in which the curable composition for encapsulating an optical semiconductor of the present invention can be used is not particularly 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 encapsulation of the present invention for sealing the optical semiconductor element. A typical cross-sectional structure is shown in FIGS.

  In the optical semiconductor device (light emitting device) 10 of FIG. 1, a mortar-shaped recess 2 ′ whose diameter gradually increases upward from the bottom surface is provided at the tip 2a of the first lead frame 2, and the recess 2 ′. The LED chip 1 is connected and fixed to the bottom surface of the LED chip 1 by die bonding via silver paste or the like, thereby electrically connecting the first lead frame 2 and one electrode (not shown) on the bottom surface of the LED chip 1. ing. The bottom surface of the recess 2 'is plated with silver. Further, the distal end portion 3 a of the second lead frame 3 and the other electrode (not shown) on the upper surface of the LED chip 1 are electrically connected via a bonding wire 4.

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

  The LED chip 1, the top end 2 a of the first lead frame 2 and the top end of the terminal portion 2 b, and the top end 3 a of the second lead frame 3 and the top end of the terminal portion 3 b have a translucent lens 6 at the tip. It is covered and sealed with the conductive resin portion 7. Further, the lower end of the terminal portion 2 b of the first lead frame 2 and the lower end of the terminal portion 3 b of the second lead frame 3 penetrate the lower end portion of the translucent resin portion 7 and protrude outside.

  In the optical semiconductor device (light emitting device) 10 ′ of FIG. 2, a mortar-shaped concave portion 8 ′ whose hole diameter gradually increases upward from the bottom surface of the package substrate 8 is provided on the bottom surface of the concave portion 8 ′. The LED chip 1 is bonded and fixed by a die bond material, 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. The bottom surface of the recess 8 'is plated with silver.

  Furthermore, in the recess 8 ′, the LED chip 1 is covered with a sealing material 5 made of a cured product obtained by curing the curable composition for optical semiconductor encapsulation 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. Such a light-emitting element is manufactured by stacking a semiconductor material on a substrate provided with a buffer layer of GaN, AlN, or the like, if necessary, by various methods such as MOCVD, HDVPE, and liquid phase growth. Things. Various materials can be used as the substrate in this case, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

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

  Examples of the structure of the light emitting element include a MIS junction, a pn junction, a homojunction having a PIN junction, a heterojunction, a double heterostructure, and the like. A single or multiple quantum well structure can also be used.

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

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

  One type of light emitting element may be used for monochromatic light emission, or a plurality of light emitting elements may be used for single color or multicolor light emission.

  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, a material having good ohmic mechanical connectivity with the electrode of the light emitting element is preferable. For example, gold, silver, copper, platinum, aluminum, and those as described in FIG. 1 and FIG. An example of the bonding wire 4 is an alloy. Alternatively, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Of 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.

  Furthermore, the material for forming the translucent resin portion 7 is not particularly limited as long as it is a translucent material, but an epoxy resin or a silicone resin is mainly used.

  The package substrate 8 can be manufactured using various materials. For example, polyphthalamide (PPA), polycarbonate resin, polyphenylene sulfide resin, polybutylene terephthalate resin, polyamide resin, liquid crystal polymer, epoxy resin, acrylic resin, etc. Examples thereof include resins, silicone resins, modified silicone resins, ABS resins, BT resins, and ceramics. Of these, polyphthalamide (PPA) is particularly preferable from the viewpoints of heat resistance, strength, and cost. Further, it is preferable that the package substrate 8 is 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 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 wire 4 from external force and dust. 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 diffusing member, or the like.

  As described above, since the curable composition for sealing an optical semiconductor of the present invention has a good impact resistance, the optical semiconductor device of the present invention in which the optical semiconductor element is sealed using the composition. 10, 10 'can be manufactured without damaging its components.

The curable composition for encapsulating an optical semiconductor of the present invention is excellent in impact resistance and crack resistance, and can provide a cured product having lower gas permeability. For example, when the optical semiconductor device is aligned in a certain direction and posture using a bowl-type vibrating part feeder during the manufacturing process, even if the optical semiconductor devices collide with each other, a member such as a disconnection of a bonding wire Since damage is less likely to occur, yield and productivity can be improved. In addition, even if a temperature cycle test is performed, cracks are hardly generated in the cured product, so that reliability can be improved. Furthermore, even if it is used in an environment where it is exposed to a sulfur-based gas, the sulfur-based gas does not easily pass through the cured product, so that a reduction in brightness can be suppressed.
Moreover, the curable composition for optical semiconductor sealing of this invention can be used suitably as a sealing material for protecting LED from the above characteristics which hardened | cured material has.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, a viscosity shows the measured value in 23 degreeC prescribed | regulated to JISK7117-1: 1999.

Example 1
A toluene solution (platinum) of a platinum-divinyltetramethyldisiloxane complex was added to 100 parts by mass of a linear polyfluoro compound represented by the following formula (27) (viscosity: 10,900 mPa · s, vinyl group content: 0.0123 mol / 100 g). (Concentration 0.5% by mass) 0.15 part by mass, 1-ethynyl-1-hydroxycyclohexane 60% toluene solution 0.20 part by mass, organohydrogenpolysiloxane represented by the following formula (28) (SiH group amount 0 0.0009 mol / g) 11.3 parts by mass, 2.0 parts by mass of a cyclic organopolysiloxane represented by the following formula (29), and 0.50 part by mass of a carboxylic acid anhydride represented by the following formula (30) And mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

(Example 2)
A toluene solution (platinum) of a platinum-divinyltetramethyldisiloxane complex was added to 100 parts by mass of a linear polyfluoro compound represented by the following formula (31) (viscosity 4,010 mPa · s, vinyl group amount 0.0299 mol / 100 g). 0.15 parts by mass), 0.20 part by mass of 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, fluorine-containing organohydrogenpolysiloxane represented by the following formula (32) (SiH group) (Amount 0.00190 mol / g) 15.7 parts by mass, 2.5 parts by mass of a cyclic organopolysiloxane represented by the following formula (33), 0.30 part by mass of a carboxylic acid anhydride represented by the following formula (34) It added sequentially and mixed so that it might become uniform. Then, the composition was prepared by performing defoaming operation.

(Example 3)
A toluene solution (platinum) of a platinum-divinyltetramethyldisiloxane complex was added to 100 parts by mass of a linear polyfluoro compound represented by the following formula (35) (viscosity 4,150 mPa · s, vinyl group amount 0.0603 mol / 100 g). (Concentration 0.5% by mass) 0.15 part by mass, 1-ethynyl-1-hydroxycyclohexane 60% toluene solution 0.20 part by mass, organohydrogenpolysiloxane represented by the following formula (36) (SiH group content 0) .00193 mol / g) 31.2 parts by mass, 3.0 parts by mass of a cyclic organopolysiloxane represented by the following formula (37), and 0.40 part by mass of a carboxylic acid anhydride represented by the following formula (38) And mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

Example 4
A toluene solution (platinum) of a platinum-divinyltetramethyldisiloxane complex was added to 100 parts by mass of a linear polyfluoro compound represented by the following formula (39) (viscosity 4,310 mPa · s, vinyl group content 0.0909 mol / 100 g). (Concentration 0.5% by mass) 0.15 parts by mass, 0.20 part by mass of 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, organohydrogenpolysiloxane represented by the following formula (40) (SiH group amount 0) 0.0016 mol / g) 46.4 parts by mass, 3.0 parts by mass of cyclic organopolysiloxane represented by the following formula (41), and 0.30 parts by mass of carboxylic acid anhydride represented by the following formula (42) And mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

(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 platinum-divinyltetramethyldisiloxane complex toluene solution (platinum concentration: 0.5% by mass), 1-ethynyl 0.20 parts by mass of a 60% toluene solution of -1-hydroxycyclohexane, 50.0 parts by mass of a linear polyfluoro compound represented by the above formula (35), an organohydrogenpolysiloxane represented by the following formula (45) ( (SiH group amount 0.00150 mol / g) 30.1 parts by mass, cyclic organopolysiloxane represented by the above formula (41) 3.0 parts by mass, carboxylic acid anhydride represented by the above formula (42) 0.30 parts by mass Portions were added sequentially and mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

(Example 6)
A toluene solution of a platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass) 0.15 parts by mass, 1-ethynyl, to 25.0 parts by mass of the linear polyfluoro compound represented by the above formula (31) 0.20 parts by mass of a 60% toluene solution of -1-hydroxycyclohexane, 75.0 parts by mass of a linear polyfluoro compound represented by the above formula (39), and an organohydrogenpolysiloxane 39 represented by the above formula (32) .8 parts by mass, 3.0 parts by mass of the cyclic organopolysiloxane represented by the above formula (41), and 0.30 parts by mass of the carboxylic acid anhydride represented by the above formula (42) are sequentially added so as to be uniform. Mixed. Then, the composition was prepared by performing defoaming operation.

(Example 7)
To 100 parts by mass of the linear polyfluoro compound represented by the above formula (31), 0.20 parts by mass of a platinum-divinyltetramethyldisiloxane complex toluene solution (platinum concentration: 0.5% by mass), 1-ethynyl-1 -0.25 parts by mass of a 60% toluene solution of hydroxycyclohexane, 53.3 parts by mass of an organohydrogenpolysiloxane represented by the above formula (32), 3.5 parts by mass of a cyclic organopolysiloxane represented by the above formula (33) Then, 0.50 parts by mass of the carboxylic acid anhydride represented by the above formula (34) and 20.0 parts by mass of the cyclic organopolysiloxane represented by the following formula (43) (vinyl group amount: 0.357 mol / 100 g) were sequentially added. And mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

(Example 8)
To 100 parts by mass of the linear polyfluoro compound represented by the above formula (35), 0.20 parts by mass of a platinum-divinyltetramethyldisiloxane complex toluene solution (platinum concentration: 0.5% by mass), 1-ethynyl-1 -0.25 parts by mass of a 60% toluene solution of hydroxycyclohexane, 89.7 parts by mass of the organohydrogenpolysiloxane represented by the above formula (36), 3.5 parts by mass of the cyclic organopolysiloxane represented by the above formula (37) Then, 0.60 part by mass of the carboxylic acid anhydride represented by the above formula (38) and 25.0 parts by mass of the cyclic organopolysiloxane represented by the following formula (44) (vinyl group content 0.451 mol / 100 g) were sequentially added. And mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

Example 9
To 100 parts by mass of the linear polyfluoro compound represented by the above formula (39), 0.25 parts by mass of a platinum-divinyltetramethyldisiloxane complex toluene solution (platinum concentration: 0.5% by mass), 1-ethynyl-1 -0.30 part by mass of a 60% toluene solution of hydroxycyclohexane, 115 parts by mass of the organohydrogenpolysiloxane represented by the above formula (40), 4.0 parts by mass of the cyclic organopolysiloxane represented by the above formula (41), 0.60 part by mass of the carboxylic acid anhydride represented by the formula (42) and 30.0 parts by mass of the cyclic organopolysiloxane represented by the above formula (44) were sequentially added and mixed uniformly. Then, the composition was prepared by performing defoaming operation.

(Example 10)
25.0 parts by mass of the linear polyfluoro compound represented by the above formula (31), 0.25 parts by mass of a platinum-divinyltetramethyldisiloxane complex toluene solution (platinum concentration: 0.5% by mass), 1-ethynyl 0.30 parts by mass of a 60% toluene solution of -1-hydroxycyclohexane, 75.0 parts by mass of a linear polyfluoro compound represented by the above formula (39), and an organohydrogenpolysiloxane 111 represented by the above formula (32) Parts by mass, 4.0 parts by mass of a cyclic organopolysiloxane represented by the above formula (41), 0.60 parts by mass of a carboxylic anhydride represented by the above formula (34), and a cyclic organopolysiloxane represented by the above formula (44) 30.0 parts by mass of siloxane were sequentially added and mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

(Comparative Example 1)
In Example 2, the addition amount of the organohydrogenpolysiloxane represented by the above formula (32) was changed to 128 parts by mass, and further 60.0 parts by mass of the cyclic organopolysiloxane represented by the above formula (43) was added. A composition was prepared in the same manner as in Example 2 except that.

(Comparative Example 2)
In Example 2, the organohydrogenpolysiloxane represented by the above formula (32) was replaced by the organohydrogenpolysiloxane represented by the following formula (46) (SiH group amount 0.00499 mol / g) 5.99 parts by mass. A composition was prepared in the same manner as in Example 2 except that the above was changed.

(Comparative Example 3)
In Example 2, the organohydrogenpolysiloxane represented by the above formula (32) was replaced by 14.2 parts by mass of the organohydrogenpolysiloxane represented by the following formula (47) (SiH group amount 0.00210 mol / g). A composition was prepared in the same manner as in Example 2 except that the above was changed.

(Comparative Example 4)
In Example 2, the organohydrogenpolysiloxane represented by the above formula (32) was changed to 24.1 parts by mass of the organohydrogenpolysiloxane represented by the above formula (46). A composition was prepared in the same manner as in Example 2 except that 20.0 parts by mass of the indicated cyclic organopolysiloxane was added.

(Comparative Example 5)
In the above Example 2, the organohydrogenpolysiloxane represented by the above formula (32) was changed to 57.2 parts by mass of the organohydrogenpolysiloxane represented by the above formula (47), and the above formula (44) A composition was prepared in the same manner as in Example 2 except that 20.0 parts by mass of the indicated cyclic organopolysiloxane was added.

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

1. Viscosity of the 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 prepared and measured according to JIS K6253-3: 2012.

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

4). Water vapor permeability: A sheet-like cured product having a thickness of 1 mm was prepared and measured using a L80-5000 type water vapor permeability meter manufactured by Lyssy in accordance with JIS K7129: 2008. The measurement temperature is 40 ° C., and the area of the cured product used for the measurement is 50 cm ² .

5. Impact resistance of cured product: In an optical semiconductor device having the same configuration as that of FIG. 2, the concave portion 8 is formed so that the LED chip 1 is immersed in the composition obtained above to form the sealing material 5. And then heated at 150 ° C. for 5 hours to produce an optical semiconductor device in which the LED chip 1 was sealed with a cured product of the composition. Then, after 1,000 optical semiconductor devices were aligned using a bowl-type vibrating parts feeder, the number of broken bonding wires was counted.

6). Crack resistance of cured product: using 10 optical semiconductor devices produced in the same manner as described above, letting it stand at −40 ° C. for 10 minutes, and then leaving it at 100 ° C. for 10 minutes as one cycle. A temperature cycle test was repeated for 500 cycles. After the test, the appearance of the cured product was visually observed, and the number of cracks was counted.

7). Gas permeability of the cured product: After the optical semiconductor device produced in the same manner as described above was left in a hydrogen sulfide gas atmosphere of 10 ppm at 100 ° C. for 100 hours, the degree of discoloration of silver on the bottom surface of the recess 8 ′ was visually observed. confirmed.

  From the results of Tables 1 and 2, the cured products obtained by curing the curable compositions for sealing an optical semiconductor (Examples 1 to 10) of the present invention have better resistance to resistance than Comparative Examples 1 to 5. Since it has impact properties, crack resistance and low gas permeability, no disconnection of the bonding wire, generation of cracks, or silver discoloration was observed.

  From the above results, it is clear that if the curable composition for sealing an optical semiconductor of the present invention is used, a cured product having excellent impact resistance and crack resistance and further low gas permeability can be obtained. It was shown that such a curable composition for encapsulating an optical semiconductor is suitable as a sealing material for an optical semiconductor element.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

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

Claims (15)

(A) A straight chain 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 -Like polyfluoro compound: 100 parts by mass,
(B) an organohydrogenpolysiloxane represented by the following general formula (1),

(Wherein, a is an integer of 3 to 10, A is a divalent organic group containing a perfluoroalkylene group, a perfluorooxyalkylene group, or both, D is independently of each other a silicon atom, A substituted or unsubstituted divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom; R ¹ is a substituted or unsubstituted monovalent hydrocarbon group independently of each other; and R ² is independently of each other. A hydrogen atom, or a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. And three or more of R ² are hydrogen atoms.)
(C) Platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom,
(D) Cyclic organopolysiloxane represented by the following general formula (2): 0.10 to 10.0 parts by mass,

(In the formula, b is an integer of 1 to 6, c is an integer of 1 to 4, d is an integer of 1 to 4, b + c + d is an integer of 4 to 10, and R ³ is independent of each other. Substituted or unsubstituted monovalent hydrocarbon group, and E is independently monovalent bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. An epoxy group or trialkoxysilyl bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom, independently of each other, and G is a perfluoroalkyl group or a monovalent perfluorooxyalkyl group However, the order of bonding of — (SiO) (H) R ³ —, — (SiO) (E) R ³ —, and — (SiO) (G) R ³ — is not limited. )
(E) Carboxylic anhydride: a curable composition for sealing an optical semiconductor containing 0.010 to 10.0 parts by mass, wherein the blending amount of the component (B) is included in the composition. The amount of hydrogen atoms directly bonded to the silicon atom in the component (B) is 0.50 to 2.0 mol with respect to 1 mol of the alkenyl group, and the curable composition for optical semiconductor encapsulation is cured. The hardened | cured material obtained by this is set to the value of 30-90 by the type A durometer prescribed | regulated to JISK6253-3: 2012, The curable composition for optical semiconductor sealing characterized by the above-mentioned. Furthermore, 0.10-50.0 mass parts of cyclic organopolysiloxane represented by following General formula (3) is included as (F) component, The sclerosing | hardenable for optical semiconductor sealing of Claim 1 characterized by the above-mentioned. Composition.

(In the formula, e is an integer of 1 to 4, f is an integer of 3 to 6, e + f is an integer of 4 to 10, and R ⁴ is independently a substituted or unsubstituted monovalent carbonization. Each independently represents a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl group bonded to the silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom or a nitrogen atom. A fluorooxyalkyl group, and L is an alkenyl group directly bonded to a silicon atom independently of each other, provided that the bonding order of — (SiO) (J) R ⁴ — and — (SiO) (L) R ⁴ — Is not limited.) The said (A) component is a linear polyfluoro compound represented by following General formula (4), The curable composition for optical semiconductor sealing of Claim 1 or Claim 2 characterized by the above-mentioned.

Wherein R ⁶ and R ⁷ are each independently an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group, and one or more are alkenyl groups. R ⁸ is independently , A hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group, g and h are each an integer of 1 to 150, an average value of g + h is 2 to 300, and i is 0 to 0 (It is an integer of 6.) The component (A) is one or more linear polyfluoro compounds selected from the group consisting of the following general formula (5), the following general formula (6), and the following general formula (7). The curable composition for optical semiconductor encapsulation according to any one of claims 1 to 3.

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

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

(Wherein R ⁸ , g, h and i are the same as above). The perfluorooxyalkylene group contained in A of the component (B) is a group containing 1 to 500 repeating units represented by the following general formula (8). The curable composition for optical semiconductor sealing of any one of these.
-C _{e '} F _2e' O- (8)
(Wherein e ′ is an integer of 1 to 6 independently for each unit) The A of the component (B) is a group selected from the group consisting of the following general formula (9), the following general formula (10), and the following general formula (11). Item 6. The curable composition for sealing an optical semiconductor according to any one of Items 5.

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

(In the formula, p is an integer of 1 to 200, and j is the same as above.)

(Wherein R ¹⁰ , j, k, and n are the same as described above. The order of bonding of each repeating unit is not limited.) The component (E) is a carboxylic acid anhydride selected from the group consisting of the following general formula (12) and the following general formula (13). The curable composition for optical semiconductor sealing of description.

(In the formula, q is an integer of 1 to 6, r is an integer of 1 to 4, s is an integer of 1 to 4, q + r + s is an integer of 4 to 10, and R ¹¹ is independently a substituted or unsubstituted monovalent group. M 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, or a monovalent group, independently of each other And Q is a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group independently of each other, provided that — (SiO) (H) R ^11. The order of bonding of —, — (SiO) (M) R ¹¹ — and — (SiO) (Q) R ¹¹ — is not limited.)

(In the formula, R ¹¹ , M, and Q are the same as above, t is an integer of 1 to 3, u is an integer of 0 to 2, and t + u is 3.) The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in the component (B) and / or the component (D) is independently represented by the following general formula (14) or general formula (15). The curable composition for sealing an optical semiconductor according to claim 1, wherein the curable composition is for sealing an optical semiconductor.
C _v F _{2v + 1} − (14)
(In the formula, v is an integer of 1 to 10.)

(Wherein w is an integer of 1 to 10) When the curable composition for sealing an optical semiconductor according to any one of claims 2 to 7 contains the component (F), the monovalent perfluoroalkyl in the component (F) group or monovalent perfluorooxyalkyl group, independently of each other the following general formula (14) or the general formula for encapsulating an optical semiconductor curable composition you wherein a group represented by (15).
C _v F _{2v + 1} − (14)
(In the formula, v is an integer of 1 to 10.)

(Wherein w is an integer of 1 to 10) The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in the component (E) is a group represented by the following general formula (14) or general formula (15) independently of each other. The curable composition for optical semiconductor encapsulation according to claim 7.
C _v F _{2v + 1} − (14)
(In the formula, v is an integer of 1 to 10.)

(Wherein w is an integer of 1 to 10) The water vapor permeability of a 1 mm-thick cured product obtained by curing the curable composition for optical semiconductor encapsulation is 15.0 g / m ² · day or less. The curable composition for optical semiconductor sealing of any one of these.   The viscosity of the curable composition for encapsulating an optical semiconductor at 23 ° C as defined in JIS K7117-1: 1999 is 50.0 to 50,000 mPa · s. 11. The curable composition for sealing an optical semiconductor according to any one of 11.   A cured product obtained by curing the curable composition for encapsulating an optical semiconductor has a refractive index of 1.30 or more and less than 1.40 at 25 ° C. and 589 nm (sodium D-line). The curable composition for optical semiconductor sealing of any one of Claims 1-12.   An optical semiconductor element and a cured product obtained by curing the curable composition for encapsulating an optical semiconductor according to any one of claims 1 to 13 for encapsulating the optical semiconductor element. An optical semiconductor device comprising:   The optical semiconductor device according to claim 14, wherein the optical semiconductor element is a light emitting diode.

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