KR20140057167A - Curable composition for sealing optical semiconductor and optical semiconductor device using the same - Google Patents

Abstract

The present invention provides a curable composition for a sealing semiconductor and an optical semiconductor device using the same. The curable composition for a sealing semiconductor is highly impact-resistant and adhesive. An optical semiconductor element of the optical semiconductor device is sealed by a cured material obtained by curing the curable composition for a sealing semiconductor. The curable composition for a sealing semiconductor includes: (A) straight-chain polyfluoro compounds; (B) fluorine-containing organo hydrogen siloxane having a SiH group and a fluorine-containing organic group; (C) a platinum group metal-based catalyst; (D) a cyclic organosiloxane having a SiH group, a fluorine-containing organic group, and an epoxy group. Type A durometer hardness, defined by JIS K6253-3, of the cured material is 30-80.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition for optical semiconductor encapsulation, and a photosemiconductor device using the same. BACKGROUND ART < RTI ID = 0.0 >

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

Conventionally, as the curable composition, a linear fluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain, a linear fluoropolyether compound having two or more hydrogen atoms directly connected to a silicon atom in one molecule It has been proposed to obtain a cured product excellent in balance of properties such as heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency and low temperature characteristics from a composition containing a fluorine-containing organohydrogensiloxane and a platinum group compound Document 1).

A composition having a self-adhesive property 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 has been proposed (Patent Document 2).

Further, there has been proposed a composition in which a carboxylic acid anhydride is added to the composition to improve adhesiveness to various substrates, particularly polyphenylene sulfide resin (PPS) or polyamide resin (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.

Also disclosed is a composition for providing a cured product having improved acid resistance than a cured product obtained from the above-described compositions described in the above Patent Documents 1 to 4, wherein the straight-chain fluoropolyether compound is a fluorine-containing polymer represented by the following formula (1) (Patent Documents 5 to 7).

(Wherein R ¹ is independently of each other a vinyl group or an alkyl group having 1 to 4 carbon atoms, R ² is independently an alkylene group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a fluorine- 1 to 4 alkyl group, Rf ¹ is a perfluoroalkylene group or a divalent perfluoropolyether group)

However, among the cured products obtained by curing the compositions actually produced in these prior arts, those having a type A durometer hardness as low as about 20 specified in JIS K6253-3 are referred to as light emitting diodes (hereinafter referred to as "LEDs" ), The impact resistance as a sealing material was sometimes insufficient. For example, when a bulk optical semiconductor device in which an LED is sealed with the cured product is aligned in a specific direction and attitude using a bowl-shaped vibrating parts feeder, the optical semiconductor devices collide with each other There is a problem that the bonding wire connecting the LED chip and the electrode is disconnected due to an impact.

On the other hand, when the hardness of the cured product is made too high to improve the impact resistance, there arises a problem that the adhesive property of the cured product to the package material of LED, particularly polyphthalic acid amide (PPA) which is a typical material, becomes insufficient .

Japanese Patent No. 2990646 Japanese Patent No. 3239717 Japanese Patent No. 3567973 Japanese Patent Application Laid-Open No. 2009-277887 Japanese Patent Laid-Open Publication No. 2011-201940 Japanese Patent Application Laid-Open No. 2011-219692 Japanese Patent Application Laid-Open No. 2002-021074

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a curable composition for optical semiconductor encapsulation that provides a cured product having excellent impact resistance and good adhesiveness and a cured product obtained by curing the curable composition for optical semiconductor encapsulation And an optical semiconductor device in which an optical semiconductor element is sealed.

In order to solve the above problems, according to the present invention,

(A) 100 parts by weight of a linear polyfluoro compound represented by the following formula (2) and / or the following formula (3) and having a vinyl group content of 0.0250 to 0.200 mol / 100 g,

(Wherein R ⁴ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, m and n are each an integer of 1 to 100, and r is an integer of 0 to 6)

(Wherein R ⁵ is an alkylene group having 1 to 6 carbon atoms, R ⁶ is a hydrogen atom or a fluorine-substituted alkyl group having 1 to 4 carbon atoms, and m, n and r are as defined above)

(B) a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom in a molecule, or a divalent perfluoro (A) a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (SiH groups) directly connected to a silicon atom and having no other functional groups in the molecule, and a fluorine-containing organohydrogensiloxane having an alkylene group or a divalent perfluorooxyalkylene group, The amount of the hydrogen atom directly connected to the silicon atom relative to 1 mole of the vinyl group of the component is 0.1 to 2.0 moles,

(C) platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom,

(D) a divalent hydrocarbon group having at least one hydrogen atom (SiH group) directly connected to a silicon atom in one molecule and further containing an oxygen atom or a nitrogen atom, represented by the following formula (4) 0.10 to 10.0 parts by mass of a cyclic organopolysiloxane having an epoxy group bonded to a silicon atom through a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to an atom and a bivalent hydrocarbon group which may contain an oxygen atom,

(Wherein i is an integer of 1 to 6, j is an integer of 1 to 4, k is an integer of 1 to 4, i + j + k is an integer of 4 to 10, R ⁷ is a substituted or unsubstituted monovalent D is a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom, E is a divalent group which may contain an oxygen atom An epoxy group bonded to a silicon atom through a hydrocarbon group)

Wherein the hardness of the cured product obtained by curing is 30 to 80 in the type A durometer specified in JIS K6253-3. The present invention also provides a curable composition for optical semiconductor encapsulation.

The curable composition for optical semiconductor encapsulation, which is the addition curing type fluoropolyether curable composition containing all the components (A) to (D) and having a hardness of the above range, is excellent in impact resistance and adhesiveness Provide a cured product.

Further, as the component (E), a divalent hydrocarbon having at least one hydrogen atom (SiH group) directly connected to a silicon atom in one molecule and having an oxygen atom or a nitrogen atom represented by the following formula (5) 0.010 to 10.0 parts by mass of a cyclic organopolysiloxane having a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a group and a cyclic anhydride carboxylic acid residue bonded to a silicon atom through a divalent hydrocarbon group,

(Wherein x is an integer of 1 to 6, y is an integer of 1 to 4, z is an integer of 1 to 4, x + y + z is an integer of 4 to 10, R ⁸ is a substituted or unsubstituted monovalent S is a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom, T is a monovalent perfluoroalkoxy group bonded to a silicon atom through a divalent hydrocarbon group A cyclic anhydride carboxylic acid residue)

Is preferably contained.

The curable composition for optical semiconductor encapsulation containing the component (E) and the components (A) to (D) can be used as a curable composition for sealing various substrates, particularly, . Therefore, the cured product of the curable composition for optical semiconductor encapsulation is suitable for a sealing material of an optical semiconductor device, particularly, a sealing material for protecting an LED.

The viscosity of the curable composition for optical semiconductor encapsulation at 23 캜 specified in JIS K7117-1 is preferably 50.0 to 50,000 mPa · s.

As described above, when the viscosity is 50.0 mPa · s or more, the flowability is too high to control the dispenser for discharging a certain amount into the LED package. Therefore, when the viscosity is 50,000 mPa · s or less, the curable composition for optical- This is preferable because it takes time to level-up in the package and there is no possibility that the productivity is lowered.

Further, it is preferable that the cured product obtained by curing the above-mentioned curable composition for optical semiconductor encapsulation has a refractive index of 1.30 or more and 1.40 or less at 25 DEG C and 589 nm (D line of sodium).

In the optical semiconductor device in which the optical semiconductor element is sealed by the cured product obtained by curing the composition of the present invention, if the refractive index is within the above range, the efficiency of extracting the light emitted from the LED to the outside It is preferable because it is not likely to be deteriorated by the design of the optical semiconductor device.

The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group of each of the component (B), the component (D) and the component (E) is represented by the following chemical formula (6) or chemical formula (7) .

(Wherein f is an integer of 1 to 10)

(Wherein g is an integer of 1 to 10)

As such, it is preferable that the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group is represented by the above formula (6) or the above formula (7).

Further, the present invention provides an optical semiconductor device and a photosemiconductor device having a cured product obtained by curing the optical semiconductor device for sealing the optical semiconductor device.

The curable composition for optical semiconductor encapsulation of the present invention can provide a cured product having good impact resistance and various substrates, particularly, good adhesion to polyphthalic acid amide (PPA), so that the optical semiconductor element When a sealed optical semiconductor device is aligned in a certain direction and posture using, for example, a ball type vibration parts feeder in its manufacturing process, even if the optical semiconductor devices collide with each other, And it is difficult to cause peeling between the cured product and the package material of the optical semiconductor device, so that the yield and productivity can be improved.

In addition, the optical semiconductor device is preferably a light emitting diode.

Thus, the cured product of the curable composition for optical semiconductor encapsulation of the present invention is particularly suitable as a sealing material for protecting the light emitting diode.

The curable composition for optical semiconductor encapsulation of the present invention has good impact resistance by having the cured product have appropriate hardness by combining the above components (A) to (D) and, if necessary, component (E) The optical semiconductor device in which the optical semiconductor element is sealed can be manufactured without damaging the member for disconnection of the bonding wire. In addition, since the curable composition for optical semiconductor encapsulation exhibits good adhesion to various substrates, particularly polyphthalic acid amide (PPA), it is suitable as a sealing material for protecting the LED.

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

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

As described above, a curable composition for optical semiconductor encapsulation which provides a cured product having good impact resistance and which has good adhesiveness to various substrates, particularly PPA, and a cured product obtained by curing the composition, A sealed optical semiconductor device is required.

The inventors of the present invention have conducted intensive studies in order to achieve the above object. As a result, they have found that a composition comprising the following components (A) to (D) Accordingly, it has been found that the curable composition for optical semiconductor encapsulation provides a cured product having an appropriate hardness, good impact resistance and good adhesiveness as an effect of the combination of the component (E), and completed the present invention . Hereinafter, the present invention will be described in detail.

[Component (A)

The component (A) of the present invention is a linear polyfluoro compound represented by the following formula (2) and / or (3) and having a vinyl group content of 0.0250 to 0.200 mol / 100 g.

(Wherein R ⁴ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, m and n are each an integer of 1 to 100, and r is an integer of 0 to 6)

(Wherein R ⁵ is an alkylene group having 1 to 6 carbon atoms, R ⁶ is independently a hydrogen atom or a fluorine-substituted alkyl group having 1 to 4 carbon atoms, and m, n and r are as defined above)

In the case of other than hydrogen atoms, R ⁴ is preferably a monovalent hydrocarbon group of 1 to 12 carbon atoms, especially 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, , An octyl group; Aryl groups such as phenyl and tolyl; Aralkyl groups such as a benzyl group and a phenylethyl group, and substituted monovalent hydrocarbon groups obtained by substituting a part or all of hydrogen atoms of these groups with a halogen atom such as fluorine. Of these, a methyl group is particularly preferable.

R ⁵ is an alkylene group having 1 to 6 carbon atoms, preferably 3 to 6 carbon atoms, and specifically includes a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, And a hexamethylene group. Particularly, a propylene group (trimethylene group, methylethylene group) is preferable.

R ⁶ is independently a hydrogen atom or a fluorine-substituted alkyl group having 1 to 4 carbon atoms, and examples of the fluorine-substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, And a group in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms, such as trifluoromethyl group. Among them, a hydrogen atom is preferable.

M and n are each an integer of 1 to 100, preferably an integer of 1 to 80, and r is an integer of 0 to 6, preferably an integer of 0 to 4.

The vinyl group content in the linear polyfluoro compound represented by the above formula (2) or (3) is preferably 0.0250 to 0.200 mol / 100 g, and more preferably 0.0280 to 0.150 mol / 100 g. When the vinyl group content is less than 0.0250 mol / 100 g, the degree of crosslinking becomes insufficient and curing problems arise. When the vinyl group content exceeds 0.200 mol / 100 g, the mechanical properties of the cured product as rubber elastomer There is a concern.

Specific examples of the straight-chain polyfluoro compound represented by the formula (2) include those represented by the following formulas.

(Wherein m and n are each an integer of 1 to 100)

Specific examples of the linear polyfluoro compound represented by the above formula (3) include those represented by the following formulas.

(Wherein m and n are each an integer of 1 to 100)

The viscosity (23 ° C) of the linear polyfluoro compound represented by the above formula (2) or (3) is 500 to 100,000 mPa · s, more preferably 1,000 to 1,000,000 mPa · s as measured by the viscosity specified in JIS K7117-1 To 50,000 mPa · s is preferable for using the composition of the present invention as a sealing material for an LED.

These linear polyfluoro compounds may be used singly or in combination of two or more. That is, one of the linear polyfluoro compounds represented by the above formula (2) or (3) can be used alone, or two or more thereof can be used in combination, May be used in combination.

[Component (B)] [

(B) is a compound having a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom in one molecule, A fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (SiH groups) directly connected to a silicon atom and having no other functional group in the molecule, a perfluoroalkylene group or a divalent perfluorooxyalkylene group, , Preferably one or more monovalent or divalent fluorine-containing organic groups in the molecule, and at least one hydrogen atom directly bonded to the silicon atom and having a hydrogen atom bonded to the silicon atom through a divalent hydrocarbon group which may contain an oxygen atom Containing epoxy group or a cyclic anhydride carboxylic acid residue bonded to a silicon atom via a divalent hydrocarbon group, or the like, which does not have a functional group other than the SiH group Kano hydrogen siloxane, to function as a crosslinking agent of the component (A).

The monovalent perfluoroalkyl group, the monovalent perfluorooxyalkyl group, the divalent perfluoroalkylene group and the divalent perfluorooxyalkylene group are preferable because of compatibility with the component (A), dispersibility and uniformity after curing It is a period introduced from the standpoint of gender.

Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include groups represented by the following formulas (6) and (7).

(Wherein f is an integer of 1 to 10, preferably 3 to 7)

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

Examples of the divalent perfluoroalkylene group or divalent perfluorooxyalkylene group include groups represented by the following formulas (8) to (10).

(Wherein p is an integer of 1 to 20, preferably an integer of 2 to 10)

(Wherein q and r are each an integer of 1 or more, preferably an integer of 1 to 100, the average of the sum of q and r is 2 to 200, preferably 2 to 100)

(Wherein s and t are each an integer of 1 to 50, preferably an integer of 1 to 30)

The perfluoroalkyl group, the perfluoroalkylene group, the perfluoroalkylene group or the perfluorooxyalkylene group and the silicon atom are preferably connected to each other by a divalent linking group, and as the divalent linking group, an alkylene group, An arylene group and a combination thereof, or an ether-bonded oxygen atom, an amide bond, a carbonyl bond, an ester bond or the like may be interposed between these groups,

, And the like.

The monovalent or divalent fluorine-containing organic group in the fluorine-containing organohydrogenpolysiloxane as the component (B) and the monovalent substituent bonded to the silicon atom other than the hydrogen atom directly bonded to the silicon atom may be a An unsubstituted or substituted alkyl or aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl and decyl; An aryl group such as a phenyl group, a tolyl group and a naphthyl group, and an aryl group in which a part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a chlorine atom, a cyano group or the like, for example, a chloromethyl group, And unsubstituted or substituted monovalent hydrocarbon groups of 1 to 20 carbon atoms. Of these, a methyl group is preferable.

As the fluorine-containing organohydrogensiloxane of the component (B), cyclic, straight-chain, three-dimensional network and combinations thereof may be used. The number of silicon atoms of the fluorine-containing organohydrogensiloxane is not particularly limited, but is usually about 2 to 60, preferably about 3 to 30.

Examples of the component (B) include those represented by the following formulas (11) to (17).

(In the formula, G is as in the above, an oxygen atom or a perfluoroalkyl group or a monovalent through a divalent hydrocarbon group which may contain a nitrogen atom by a monovalent perfluoroalkyl group bonded to a silicon atom independently oxyalkyl group, R ⁹ are independently Unsubstituted or substituted alkyl group or aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and s is an integer of 2 to 6, preferably an integer of 3 to 6, and t is 1 Preferably an integer of 1 to 3, and s + t is an integer of 4 to 10, preferably an integer of 4 to 9,

(Wherein J is independently the same as G above, R ¹⁰ is independently the same as R ^9, and p 'is an integer of 2 to 50, preferably an integer of 3 to 30)

(Wherein q 'is an integer of 1 to 40, preferably an integer of 1 to 20, and p' + q 'is an integer of 4 to 60, preferably an integer of 4 to 50)

(Wherein r 'is an integer of 1 to 40, preferably an integer of 1 to 20, and p' + r 'is an integer of 4 to 60, preferably an integer of 4 to 50)

(Wherein p '+ q' + r 'is an integer of 5 to 60, preferably an integer of 5 to 50)

(Wherein L is an oxygen atom, an alkylene group, a divalent perfluoroalkylene group bonded to a silicon atom through a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a divalent perfluorooxyalkylene group, M is independently the same as G, R ¹¹ is independently the same as R ⁹ , s 'is an integer of 1 to 3, t' is an integer of 1 to 3, s '+ t' Preferably an integer of 3 to 5,

(Wherein Q is the same as G and R ¹² is independently the same as R ⁹ above)

Specific examples of the component (B) include the following compounds. These compounds may be used alone, or two or more of them may be used in combination. In the following formula, Me represents a methyl group and Ph represents a phenyl group.

The component (B) may be used singly or in combination of two or more. The compounding amount of the component (B) is such that the hydrogen atom directly connected to the silicon atom in the component (B) is 0.1 to 2.0 moles, more preferably 0.5 to 1.5 moles, relative to 1 mole of the vinyl group of the component (A). When the SiH group is less than 0.1 mol, the degree of crosslinking is insufficient. On the other hand, if it exceeds 2.0 mol, the storage stability may be impaired or the heat resistance of the cured product obtained after curing may be lowered.

[Component (C)] [

The platinum group metal catalyst as component (C) of the present invention is a hydrosilylation catalyst. The hydrosilylation reaction catalyst is a catalyst for promoting the addition reaction between an alkenyl group contained in the composition, particularly, the alkenyl group in the component (A), and the SiH group contained in the composition, particularly the SiH group in the component (B). Since this hydrosilylation reaction catalyst is generally a noble metal or a compound thereof, platinum or platinum compounds which are relatively easy to obtain are often used because they are expensive.

Examples of the platinum compound include a complex of chloroplatinic acid or chloroplatinic acid with an olefin such as ethylene, a complex with an alcohol or a vinyl siloxane, and a metal platinum supported on silica, alumina, carbon or the like. Platinum or has as a platinum group metal-based catalysts other than compounds thereof, rhodium, ruthenium, iridium and palladium compounds are also known, for example, _{RhCl (PPh 3) 3, RhCl} (CO) (PPh 3) 2, Ru 3 (CO) 12 , it can be exemplified _{IrCl (CO) (PPh 3)} 2, Pd (PPh 3) 4 and the like. In the above formula, Ph is a phenyl group.

When the catalyst is used, it may be used in a solid state when it is a solid catalyst. However, in order to obtain a more uniform cured product, a solution obtained by dissolving chloroplatinic acid or a complex in an appropriate solvent such as toluene or ethanol is referred to as A ) Is preferably used in a straight-chain polyfluoro compound.

The amount of the component (C) is an effective amount as a hydrosilylation catalyst, and is 0.1 to 500 ppm, particularly preferably 0.5 to 200 ppm (in terms of mass of the platinum group metal atom) relative to the component (A) And can be appropriately increased or decreased.

[Component (D)] [

The component (D) of the present invention is a compound represented by the following formula (4), wherein a hydrogen atom directly bonded to a silicon atom in a molecule and a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom Is a cyclic organopolysiloxane having an epoxy group bonded to a silicon atom through a perfluoroalkyl group or a monovalent perfluorooxyalkyl group and a divalent hydrocarbon group which may contain an oxygen atom and which is obtained by curing the composition of the present invention To give a self-adhesive property to the film.

I is an integer of 1 to 6, preferably an integer of 2 to 5, j is an integer of 1 to 4, preferably an integer of 1 to 3, k is an integer of 1 to 4, I + j + k is an integer of 4 to 10, preferably an integer of 4 to 8,

R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the same groups as the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ⁴ .

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 is similar to the above formulas (6) and (7) . These are groups introduced from the viewpoint of compatibility with component (A), dispersibility, uniformity after curing, and the like.

E is an epoxy group bonded to a silicon atom via a bivalent hydrocarbon group which may contain an oxygen atom, and specifically includes a group represented by the following formula (18).

(In the formula, R ¹³ is a divalent hydrocarbon group of 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, in which an oxygen atom may intervene, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, An alkylene group such as an octylene group, a cycloalkylene group such as a cyclohexylene group, an oxyalkylene group such as an oxyethylene group, an oxypropylene group, and an oxybutylene group)

E is specifically exemplified by the following.

As the component (D), for example, the following compounds may be mentioned. In the following formula, Me represents a methyl group.

The component (D) may be used singly or in combination of two or more. The amount of the component (D) to be used is in the range of 0.10 to 10.0 parts by mass, preferably 0.50 to 8.0 parts by mass based on 100 parts by mass of the component (A). If it is less than 0.10 parts by mass, sufficient adhesion can not be obtained. If it exceeds 10.0 parts by mass, the fluidity of the composition is deteriorated, and the physical strength of the resulting cured product is lowered.

[Component (E)] [

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

The component (E) of the present invention is a compound represented by the following formula (5), wherein a hydrogen atom directly bonded to a silicon atom in a molecule and a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom Is a cyclic organopolysiloxane having a perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group and a cyclic anhydride carboxylic acid residue bonded to the silicon atom, To further promote the adhesive property of the cured product obtained by curing the composition of the present invention.

X is an integer of 1 to 6, preferably an integer of 2 to 5, y is an integer of 1 to 4, preferably an integer of 1 to 3, z is an integer of 1 to 4, And x + y + z is an integer of 4 to 10, preferably an integer of 4 to 8.

R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the same groups as the above-mentioned substituted or unsubstituted monovalent hydrocarbon group of R ⁴ .

S is a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom and is similar to the above-described formulas (6) and (7) . These are groups introduced from the viewpoint of compatibility with component (A), dispersibility, uniformity after curing, and the like.

T is a cyclic anhydride carboxylic acid residue bonded to a silicon atom through a divalent hydrocarbon group, and specifically includes a group represented by the following formula (19).

In the above general formula (19), R ¹⁴ is a divalent hydrocarbon group having 1 to 15 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group and a butylene group. Of these, a propylene group is preferable.

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

The component (E) may be used singly or in combination of two or more. The blending amount of the component (E) is in the range of 0.010 to 10.0 parts by mass, preferably 0.10 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). When the amount is more than 0.010 parts by mass, an effect sufficient to promote the adhesion of the composition of the present invention is obtained. When the amount is 10.0 parts by mass or less, the fluidity of the composition deteriorates and the preservation stability of the composition is not impaired.

[Other Ingredients]

In the curable composition for optical semiconductor encapsulation of the present invention, in addition to the above components (A) to (E), a plasticizer, a viscosity adjusting agent, a flexibility imparting agent, an inorganic filler, Other additives such as an adhesion promoter may be added as needed. The blending amount of these additives is arbitrary.

A polyfluoromonoalkenyl compound represented by the following chemical formula (20) and / or a linear polyfluoro compound represented by the following chemical formulas (21) and (22) are used as plasticizers, viscosity modifiers, .

[Wherein Rf is a group represented by the following formula (I)

(Wherein a 'is an integer of 1 to 200, preferably 1 to 150, and b' is an integer of 1 to 3)

X is _{-CH 2 -, -OCH 2 -,} -CH 2 OCH 2 - or -CO-NR-Y- (where, R is a hydrogen atom, a methyl group, a phenyl group or allyl, Y is -CH ₂ - to, A group represented by the structural formula (Z) or a group represented by the following structural formula (Z '), u is 0 or 1,

(, Of the formula X 'is _{C d' F 2d '+1 -} (d' is a group represented by from 1 to 3), c 'is an integer of from 1 to 200 integer, preferably from 2 to 100)

(In the formulas, X 'is as defined above, e' and f 'are each an integer of 1 to 200, preferably an integer of 1 to 100, and the sum of e' and f ' Is from 2 to 300)

Specific examples of the polyfluoromonoalkenyl compound represented by the above general formula (20) include, for example, the following.

(Where m = 1 to 100)

Specific examples of the linear polyfluoro compounds represented by the above-mentioned formulas (21) and (22) include, for example, the following.

G ', h' and i 'are each an integer of 1 to 200, preferably an integer of 1 to 150, and the average of the sum of h' and i 'is an integer of 2 to 400, preferably 2 to 300 Lt; / RTI >

The viscosity (23 ° C) of the polyfluoro compound represented by the above formulas (20) to (22) is in the range of 5.00 to 100,000 mPa · s, particularly 50.0 to 50,000 mPa · s .

Examples of the inorganic filler include silica powders such as aerosol silica, precipitated silica, spherical silica and silica airgel; or silica powders obtained by treating the surface of the silica powder with various organochlorosilanes, organosilazanes, cyclic organopolysilazanes, and the like Silica powder, and the above-mentioned surface-treated silica powder are mixed with a monovalent perfluoroalkyl group represented by the above formula (6) or an organosilane or organosiloxane having a monovalent perfluorooxyalkyl group represented by the above formula (7) A silica-based reinforcing filler such as a silica powder obtained by reprocessing an inorganic filler such as silica powder, quartz powder, fused quartz powder, diatomaceous earth, a reinforcing or quasi-reinforcing filler such as calcium carbonate, inorganic materials such as titanium oxide, iron oxide, carbon black, cobalt aluminate Pigment, titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, Syum, there may be mentioned a conductive agent such as heat-resistance improvers, alumina, boron nitride, silicon carbide, metal powder or the like of the thermal conductivity giving agent, carbon black, silver powder and conductive zinc oxide, such as manganese carbonate. Further, inorganic fine particles having a refractive index of 1.59 or less at 25 DEG C and 589 nm (D line of sodium) such as magnesium fluoride, aluminum fluoride, calcium fluoride, lithium fluoride, sodium fluoride, thorium fluoride silicon oxide and the like are also useful as a reinforcing filler.

Examples of the controlling agent for the hydrosilylation reaction catalyst include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5- -Methyl-1-penten-3-ol, phenylbutylol and the like, chlorosilanes having a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group similar to G as described above, and acetylenic alcohols 3-pentene-1-phosphorene, 3,5-dimethyl-3-hexene-1-phosphorene and triallyl isocyanurate, and polyvinylsiloxane and organic phosphorus compounds. By the addition thereof, the curing reactivity and the storage stability can appropriately be maintained.

Examples of the adhesion promoter other than the component (E) include a carboxylic acid anhydride as described below. In the following formula, Me represents a methyl group. These compounds may be used alone, or two or more of them may be used in combination.

The method for producing the curable composition for optical semiconductor encapsulation of the present invention is not particularly limited and can be produced by mixing the components (A) to (D), the component (E) and other optional components and kneading them. If necessary, a kneader such as a planetary mixer, a loss mixer, a mixing device such as a hobart mixer, a kneader, and a three-axis roll may be used .

The constitution of the curable composition for optical semiconductor encapsulation of the present invention may be constituted as a so-called single liquid type in which all of the components (A) to (D), component (E) Alternatively, they may be of a two-liquid type, and they may be mixed at the time of use.

The curable composition for optical semiconductor encapsulation of the present invention is cured by heating to have good impact resistance and to adhere very well to package materials such as polyphthalic acid amide (PPA) and liquid crystal polymer (LCP) and metal substrates, And is useful as a sealing material for protecting optical semiconductor elements such as LED, IC, LSI, and organic EL. The curing temperature of the curable composition for optical semiconductor encapsulation is not particularly limited, but is usually 20 to 250 占 폚, preferably 40 to 200 占 폚. In this case, the curing time may be appropriately selected depending on the time required for completing the crosslinking reaction and the bonding reaction with various semiconductor packaging materials. In general, the curing time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 8 hours .

The type A durometer hardness of the cured product obtained by curing the composition of the present invention specified in JIS K6253-3 is 30 to 80. If it is less than 30, the impact resistance as an LED sealing material may be deteriorated. On the other hand, if it is higher than 80, adhesion with polyphthalic acid amide (PPA) becomes difficult.

The viscosity of the composition of the present invention at 23 캜 specified in JIS K7117-1 is preferably from 50.0 to 50,000 mPa · s and more preferably from 100 to 30,000 mPa · s from the viewpoint of handling workability. When the viscosity is 50.0 mPa · s or more, the fluidity is too high, and there is no fear that control of the dispenser for discharging a certain amount into the LED package becomes difficult. When the viscosity is 50,000 mPa · s or less, the composition needs an excessive time for leveling in the LED package There is no fear that the productivity will be lowered.

The refractive index of the cured product obtained by curing the composition of the present invention at 25 DEG C and 589 nm (D line of sodium) is preferably 1.30 or more and less than 1.40. In the optical semiconductor device in which the optical semiconductor element is sealed by the cured product obtained by curing the composition of the present invention when the refractive index is within this range, the efficiency of extracting the light emitted from the LED to the outside is lowered, It is preferable because it is not likely to deteriorate according to the design of the semiconductor device.

When the composition of the present invention is used, the composition may be mixed with a suitable fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, Fluorinert (3M) , Perfluorobutyl methyl ether, perfluorobutyl ethyl ether and the like at a desired concentration.

The structure of the optical semiconductor device in which the curable composition for optical semiconductor encapsulation of the present invention can be used is not particularly limited. The optical semiconductor device of the present invention has an optical semiconductor element and a cured product obtained by curing the optical semiconductor encapsulating composition of the present invention for sealing the optical semiconductor element, .

The light semiconductor device (light emitting device) 10 of Fig. 1 has a concave portion 2 'of a trigger shape in which the hole diameter is gradually widened upward from the bottom surface of the front end portion 2a of the first lead frame 2, And the LED chip 1 is connected and fixed on the bottom surface of the concave portion 2 'by a die bond via a silver paste or the like so that the first lead frame 2 and the LED chip 1, And one electrode (not shown) of the bottom surface is electrically connected. The front end portion 3a of the second lead frame 3 is electrically connected to the other electrode (not shown) on the upper surface of the LED chip 1 through a bonding wire 4.

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

The upper end portions of the LED chip 1, the front end portion 2a of the first lead frame 2 and the terminal portion 2b and the upper end portions of the front end portion 3a and the terminal portion 3b of the second lead frame 3, And is covered and sealed by a translucent resin portion 7 having a convex lens portion 6. [ The lower end portion of the terminal portion 2b of the first lead frame 2 and the lower end portion of the terminal portion 3b of the second lead frame 3 penetrate through the lower end portion of the translucent resin portion 7 and protrude to the outside.

In the optical semiconductor device (light emitting device) 10 'shown in Fig. 2, a recessed portion 8' is formed in the upper portion of the package substrate 8, and the recessed portion 8 ' The LED chip 1 is adhered and fixed to the bottom surface of the concave portion 8 'by a die bond material and the electrode of the LED chip 1 is fixed to the package substrate 8 by the bonding wire 4 (Not shown).

In the concave portion 8 ', the LED chip 1 is covered with a sealing material 5 containing a cured product obtained by curing the above-mentioned curable composition for optical semiconductor sealing of the present invention.

Here, as the LED chip 1, a light emitting element used in a conventionally known LED chip can be used without particular limitation. Examples of such a light-emitting device include those obtained by laminating a semiconductor material on a substrate provided with a buffer layer such as GaN or AlN, if necessary, by various methods such as MOCVD, HDVPE, or liquid growth . As the substrate in this case, various materials can be used, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and GaN single crystals. Of these, sapphire is preferably used from the viewpoint of easily forming GaN with good crystallinity and high industrial value.

Examples of the semiconductor material to be laminated include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN and SiC. Of these, the nitride compound semiconductor (In _x Ga _y Al _z N) is preferable from the viewpoint of obtaining high brightness. Such materials may include activators and the like.

Examples of the structure of the light emitting device include MIS junction, pn junction, homo junction having a PIN junction, hetero junction, and double hetero structure. Further, a single or multiple quantum well structure may be used.

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

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

The light emitting element to be used may be monochromatic or monochromatic or multicolor by using a plurality of monochromatic light.

Electrodes can be formed on the light emitting device 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. It is preferable that the electrical connecting member has good ohmic mechanical connection with the electrode of the light emitting element. For example, gold, silver, copper, platinum, aluminum, alloys thereof, and the like as shown in Figs. And a bonding wire 4 using a bonding wire. A conductive adhesive filled with a conductive filler such as silver or carbon may be used. Of these, from the viewpoint of good workability, it is preferable to use an aluminum wire or a gold wire.

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.

The material for forming the light-transmissive resin portion 7 is not particularly limited as long as it is a light-transmitting material, but mainly epoxy resin or silicone resin is used.

In addition, the package substrate 8 can be manufactured using various materials such as polyphthalic acid amide (PPA), polycarbonate resin, polyphenylene sulfide resin, polybutylene terephthalate resin, polyamide resin , A liquid crystal polymer, an epoxy resin, an acrylic resin, a silicone resin, a modified silicone resin, an ABS resin, a BT resin, and a ceramic. Of these, polyphthalic acid amide (PPA) is particularly preferable in view of heat resistance, strength and cost. In addition, it is preferable that the package substrate 8 is mixed with a white pigment such as barium titanate, titanium oxide, zinc oxide, barium sulfate or the like to improve the reflectance of light.

The sealing material 5 covering the LED chip 1 efficiently transmits the light from the LED chip 1 to the outside and simultaneously transmits the light from the LED chip 1 or the bonding wire 4). 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 substance or a light diffusion member.

Since the curable composition for optical semiconductor encapsulation of the present invention has good impact resistance, the optical semiconductor device (10, 10 ') of the present invention, in which the optical semiconductor element is sealed using the composition, Can be produced.

[Example]

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, Me represents a methyl group. The viscosity refers to the measured value at 23 캜 specified in JIS K7117-1.

(Example 1)

A platinum-divinyltetramethyldisiloxane complex of a toluene solution (platinum concentration of 0.5% by mass) was added to 100 parts by mass of a linear polyfluoro compound represented by the following formula (23) (viscosity: 4,310 mPa s, vinyl group amount: 0.0909 mol / ), 0.20 parts by mass of a 60% toluene solution of 1-ethynyl-1-hydroxycyclohexane, 17.8 parts by mass of a fluorine-containing organohydrogensiloxane (SiH group amount: 0.00486 mol / And 3.0 parts by mass of a cyclic organopolysiloxane represented by the following formula (25) were successively added and mixed so as to be uniform. Thereafter, the composition was prepared by performing a defoaming operation.

(Example 2)

In Example 1, a linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (26) (viscosity: 4,250 mPa,, vinyl group amount: 0.0911 mol / A composition was prepared in the same manner as in Example 1.

(Example 3)

In Example 1, a linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (27) (viscosity 17,800 mPa,, vinyl group amount 0.0290 mol / 100 g) And the addition amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 5.67 parts by mass.

(Example 4)

In Example 1, a linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound (viscosity 17,300 mPa,, vinyl group amount 0.0289 mol / 100 g) represented by the following formula (28) , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 5.65 parts by mass.

(Example 5)

In Example 1, a linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (29) (having a viscosity of 1,720 mPa · s and a vinyl group content of 0.184 mol / 100 g) , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 36.0 parts by mass.

(Example 6)

In Example 1, the linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (30) (having a viscosity of 1,680 mPa · s and a vinyl group content of 0.181 mol / 100 g) , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 35.4 parts by mass.

(Example 7)

Except that the amount of the linear polyfluoro compound represented by the formula (23) was changed to 50.0 parts by mass and the linear polyfluoro compound represented by the formula (26) was added in an amount of 50.0 parts by mass in Example 1 Was prepared in the same manner as in Example 1.

(Example 8)

In Example 1, the amount of the linear polyfluoro compound represented by the formula (23) was changed to 60.0 parts by mass, and the linear polyfluoro compound represented by the formula (27) was added in an amount of 40.0 parts by mass, A composition was prepared in the same manner as in Example 1 except that the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 10.9 parts by mass.

(Example 9)

In Example 1, the amount of the linear polyfluoro compound represented by the formula (23) was changed to 70.0 parts by mass, and the linear polyfluoro compound represented by the formula (28) was added in an amount of 30.0 parts by mass, A composition was prepared in the same manner as in Example 1 except that the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 14.1 parts by mass.

(Example 10)

Except that in Example 1, 14.3 parts by mass of a fluorine-containing organohydrogensiloxane (SiH group amount 0.00605 mol / g) represented by the following formula (31) was added instead of the fluorine-containing organohydrogensiloxane represented by the formula (24) Was prepared in the same manner as in Example 1.

(Example 11)

Except that 56.1 parts by weight of a fluorine-containing organohydrogensiloxane (SiH group amount: 0.00154 mol / g) represented by the following formula (32) was added instead of the fluorine-containing organohydrogensiloxane represented by the formula (24) Was prepared in the same manner as in Example 1.

(Example 12)

In Example 1, 32.7 parts by mass of a fluorine-containing organohydrogensiloxane (SiH group amount 0.00264 mol / g) represented by the following formula (33) was added instead of the fluorine-containing organohydrogensiloxane represented by the formula (24) A composition was prepared in the same manner as in Example 1 except that 3.0 parts by mass of a cyclic organopolysiloxane represented by the following formula (34) was added instead of the cyclic organopolysiloxane represented by the formula (25).

(Example 13)

In Example 1, 17.7 parts by mass of a fluorine-containing organohydrogensiloxane (SiH group content 0.00488 mol / g) represented by the following formula (35) was added instead of the fluorine-containing organohydrogensiloxane represented by the formula (24) A composition was prepared in the same manner as in Example 1 except that 3.0 parts by mass of a cyclic organopolysiloxane represented by the following formula (36) was added instead of the cyclic organopolysiloxane represented by the formula (25).

(Example 14)

In Example 1, 32.7 parts by mass of a fluorine-containing organohydrogensiloxane (SiH group amount 0.00264 mol / g) represented by the following formula (37) was added instead of the fluorine-containing organohydrogensiloxane represented by the formula (24) A composition was prepared in the same manner as in Example 1 except that 3.0 parts by mass of a cyclic organopolysiloxane represented by the following formula (38) was added instead of the cyclic organopolysiloxane represented by the formula (25).

(Example 15)

A composition was prepared in the same manner as in Example 1 except that 0.50 parts by mass of a cyclic organopolysiloxane represented by the following formula (39) was added to Example 1.

(Example 16)

A composition was prepared in the same manner as in Example 2 except that 0.50 parts by mass of a cyclic organopolysiloxane represented by the following formula (40) was added in Example 2.

(Example 17)

A composition was prepared in the same manner as in Example 3 except that 0.50 parts by mass of the cyclic organopolysiloxane represented by the following formula (41) was added to the above Example 3. [

(Example 18)

A composition was prepared in the same manner as in Example 4 except that 0.70 parts by mass of a cyclic organopolysiloxane represented by the following formula (42) was added.

(Example 19)

A composition was prepared in the same manner as in Example 5 except that 0.90 part by mass of the cyclic organopolysiloxane represented by the formula (40) was added.

(Example 20)

A composition was prepared in the same manner as in Example 6 except that 0.90 part by mass of the cyclic organopolysiloxane represented by the formula (40) was added.

(Comparative Example 1)

In Example 1, 100 parts by weight of a linear polyfluoro compound represented by the formula (23) and a linear polyfluoro compound represented by the following formula (43) (viscosity: 4,010 mPa,, vinyl group amount: 0.0299 mol / 100 g) And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 5.84 parts by mass.

(Comparative Example 2)

In Example 2, a linear polyfluoro compound represented by the formula (26) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (44) (viscosity: 3,920 mPa,, vinyl group amount: 0.0296 mol / , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 5.79 parts by mass.

(Comparative Example 3)

In Example 3, the linear polyfluoro compound represented by the formula (27) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (45) (viscosity 17,100 mPa,, vinyl group amount 0.0097 mol / 100 g) And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 1.90 parts by mass.

(Comparative Example 4)

In Example 4, the linear polyfluoro compound represented by the formula (28) was mixed with 100 parts by mass of a linear polyfluoro compound (viscosity 16,800 mPa,, vinyl group amount 0.0094 mol / 100 g) represented by the following formula (46) , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 1.84 parts by mass.

(Comparative Example 5)

In Example 1, a linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (47) (viscosity 27,500 mPa,, vinyl group amount 0.0239 mol / 100 g) And the addition amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 4.67 parts by mass.

(Comparative Example 6)

In Example 1, 100 parts by weight of a linear polyfluoro compound represented by the formula (23) and a linear polyfluoro compound represented by the following formula (48) (viscosity 26,800 mPa 占 퐏, 0.0235 mol / , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 4.59 parts by mass.

(Comparative Example 7)

In Example 1, 100 parts by mass of a linear polyfluoro compound represented by the formula (23) and a linear polyfluoro compound represented by the following formula (49) (viscosity 1,510 mPa,, vinyl group amount 0.203 mol / , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 39.7 parts by mass.

(Comparative Example 8)

In Example 1, a linear polyfluoro compound represented by the formula (23) was mixed with 100 parts by mass of a linear polyfluoro compound represented by the following formula (50) (viscosity: 1,450 mPa,, vinyl group amount: 0.202 mol / , And the amount of the fluorine-containing organohydrogensiloxane represented by the formula (24) was changed to 39.5 parts by mass.

(Comparative Example 9)

In Example 15, the linear polyfluoro compound represented by the formula (23) was changed to 100 parts by mass of the linear polyfluoro compound represented by the formula (49), and the fluorine-containing polyfluoro compound represented by the formula A composition was prepared in the same manner as in Example 15 except that the addition amount of the organohydrogensiloxane was changed to 39.7 parts by mass.

(Comparative Example 10)

In Example 16, the straight-chain polyfluoro compound represented by the formula (26) was changed to 100 parts by mass of the linear polyfluoro compound represented by the formula (50), and the fluorine-containing A composition was prepared in the same manner as in Example 16 except that the addition amount of the organohydrogensiloxane was changed to 39.5 parts by mass.

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

1. Viscosity of the composition: Measured at 23 캜 according to JIS K7117-1.

2. Hardness: A sheet-like cured product having a thickness of 2 mm was prepared and measured according to JIS K6253-3.

3. Refractive index: A sheet-shaped cured product having a thickness of 2 mm was prepared and the refractive index at 58 DEG C (D line of sodium) was measured at 25 DEG C using a multi-wavelength Abbe's refractometer DR-M2 / 1550 (manufactured by Atago KABUSHIKI KAISHA) .

4. Adhesion to polyphthalic acid amide (PPA): Two 100 mm x 25 mm test panels of PPA were superimposed with a layer of the composition obtained above having a thickness of 80 mu m interposed therebetween such that the ends were overlapped by 10 mm each, The composition was cured by heating at 150 DEG C for 5 hours to prepare an adhesive test piece. Subsequently, the test piece was subjected to a tensile shear adhesion test (tensile rate: 50 mm / min) to evaluate the adhesive strength (shear adhesive strength) and the cohesive failure rate.

5. Impact resistance of the cured product: In the optical semiconductor device having the configuration similar to that of Fig. 2, the composition obtained as described above for forming the sealing material 5 is applied to the concave portion 8 'so as to immerse the LED chip 1, , And heated at 150 占 폚 for 5 hours to fabricate an optical semiconductor device in which the LED chip 1 was sealed with a cured product of the composition. Then, 1,000 optical semiconductor devices were arranged on the ball type vibrating parts feeder, and the number of the bonding wires was cut.

From the results shown in Tables 1 and 2, the cured products obtained by curing the curable compositions for optical semiconductor encapsulation (Examples 1 to 20) of the present invention had good impact resistance and good adhesion to PPA And no disconnection of the bonding wire was observed. Thus, by using the curable composition for optical semiconductor encapsulation of the present invention in the sealing material of an optical semiconductor element, it is possible to manufacture the optical semiconductor device without damaging the broken line of the bonding wire even if the optical semiconductor devices collide with each other during the manufacturing process have.

The present invention is not limited to the above-described embodiments. The above embodiment is an example, and any of those having substantially the same constitution as the technical idea described in the claims of the present invention and exhibiting similar operational effects are included in the technical scope of the present invention.

1: LED chip 2: first lead frame
2a: a front end portion of a first lead frame 2b: a terminal portion of a first lead frame
2 ': recess 3: second lead frame
3a: a tip portion of a second lead frame 3b: a terminal portion of a second lead frame
4: bonding wire 5: sealing material
6: convex lens part 7: translucent resin part
8: package substrate 8 ': concave portion
9: electrodes 10 and 10 ': optical semiconductor device

Claims (7)

(A) 100 parts by weight of a linear polyfluoro compound represented by the following formula (2) and / or the following formula (3) and having a vinyl group content of 0.0250 to 0.200 mol / 100 g,

(Wherein R ⁴ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, m and n are each an integer of 1 to 100, and r is an integer of 0 to 6)

(Wherein R ⁵ is an alkylene group having 1 to 6 carbon atoms, R ⁶ is a hydrogen atom or a fluorine-substituted alkyl group having 1 to 4 carbon atoms, and m, n and r are as defined above)
(B) a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom in a molecule, or a divalent perfluoro (A) a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (SiH groups) directly connected to a silicon atom and having no other functional groups in the molecule, and a fluorine-containing organohydrogensiloxane having an alkylene group or a divalent perfluorooxyalkylene group, The amount of the hydrogen atom directly connected to the silicon atom relative to 1 mole of the vinyl group of the component is 0.1 to 2.0 moles,
(C) platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom,
(D) a divalent hydrocarbon group having at least one hydrogen atom (SiH group) directly connected to a silicon atom in one molecule and represented by the following formula (4), and which may contain an oxygen atom or a nitrogen atom, And 0.10 to 10.0 parts by mass of a cyclic organopolysiloxane having an epoxy group bonded to a silicon atom via a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to the silicon atom and a divalent hydrocarbon group which may include an oxygen atom

(Wherein i is an integer of 1 to 6, j is an integer of 1 to 4, k is an integer of 1 to 4, i + j + k is an integer of 4 to 10, R ⁷ is a substituted or unsubstituted monovalent D is a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom, E is a divalent group which may contain an oxygen atom An epoxy group bonded to a silicon atom through a hydrocarbon group)
And the cured product obtained by curing has a hardness of 30 to 80 in the type A durometer specified in JIS K6253-3. The organic electroluminescence device according to claim 1, which further comprises at least one hydrogen atom (SiH group) directly connected to a silicon atom in one molecule, which may be an oxygen atom or a nitrogen atom, represented by the following formula (5) A monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group and a cyclic anhydropolysiloxane having a cyclic anhydride carboxylic acid residue bonded to a silicon atom through a divalent hydrocarbon group: 10.0 parts by mass

(Wherein x is an integer of 1 to 6, y is an integer of 1 to 4, z is an integer of 1 to 4, x + y + z is an integer of 4 to 10, R ⁸ is a substituted or unsubstituted monovalent S is a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom through a bivalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom, T is a monovalent perfluoroalkoxy group bonded to a silicon atom through a divalent hydrocarbon group A cyclic anhydride carboxylic acid residue)
Wherein the curable composition for optical semiconductor encapsulation further comprises a curing agent. The curable composition for optical semiconductor encapsulation according to claim 1 or 2, wherein the viscosity of the curable composition for optical semiconductor encapsulation at 23 캜 specified in JIS K7117-1 is 50.0 to 50,000 mPa.. The curable composition for optical semiconductor encapsulation according to claim 1 or 2, wherein the cured product obtained by curing the optical semiconductor encapsulating composition has a refractive index of 1.30 or more and less than 1.40 at 25 DEG C and 589 nm (D line of sodium) Composition. The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group of each of the components (B), (D) and (E) is represented by the following formula (6) or (7). ≪ / RTI >

(Wherein f is an integer of 1 to 10)

(Wherein g is an integer of 1 to 10) A optical semiconductor device characterized by having an optical semiconductor element and a cured product obtained by curing the optical semiconductor encapsulating composition according to claim 1 or 2 for sealing the optical semiconductor element. The optical semiconductor device according to claim 6, wherein the optical semiconductor element is a light emitting diode.

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