JP2012188627A - Lens material for optical semiconductor apparatus, optical semiconductor apparatus, and method for manufacturing optical semiconductor apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lens material for an optical semiconductor apparatus, which can be formed into a lens having a good lens shape, can enhance the transparency of a lens, and can cause light extracted from an optical semiconductor apparatus having a lens to be bright.SOLUTION: The material contains: a first organopolysiloxane represented by formula (1) and having an alkenyl group bonded to a silicon atom and an aryl group bonded to a silicon atom (excluding an organopolysiloxane having a hydrogen atom bonded to a silicon atom); a second organopolysiloxane represented by formula (51) and having a hydrogen atom bonded to a silicon atom and an aryl group bonded to a silicon atom; a hydrosilylating reaction catalyst; and a silicon oxide particle, wherein the content ratios of the aryl groups bonded to the silicon atoms in the first and second organopolysiloxanes are ≥3 mol% and ≤40 mol%, respectively.

Description

  The present invention relates to a liquid optical semiconductor device lens material used for forming a lens in an optical semiconductor device, an optical semiconductor device using the optical semiconductor device lens material, and a method of manufacturing the optical semiconductor device.

  An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When an optical semiconductor element (for example, an LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is generally sealed with the sealing agent.

  Further, in an optical semiconductor device, a lens may be formed using a lens material for an optical semiconductor device in order to control the light emission direction or to prevent the front luminance from becoming too high. The lens is disposed on the surface of the sealant, for example.

  Patent Document 1 listed below includes (A) an organopolysiloxane having two or more aliphatic unsaturated bonds and (B) two or more hydrogen atoms bonded to silicon atoms as the lens material for the optical semiconductor device. A lens material including an organohydrogenpolysiloxane, (C) a platinum group metal catalyst, and (D) a release agent is disclosed.

JP 2006-328103 A

  A conventional lens material for an optical semiconductor device as described in Patent Document 1 may not be able to form a lens having a good lens shape. For example, when a plurality of optical semiconductor devices having a lens is manufactured using a conventional lens material, the lens shape may vary. For this reason, the brightness of the light emitted from the obtained plurality of optical semiconductor devices may vary.

  Furthermore, in the conventional lens material, the transparency of the lens using the lens material may be low, and the brightness of light extracted from the optical semiconductor device having the lens may be low.

  An object of the present invention is to provide a lens material for an optical semiconductor device capable of forming a lens having a good lens shape, further improving the transparency of the lens, and brightening light extracted from the optical semiconductor device having the lens, and the light. An optical semiconductor device using a lens material for a semiconductor device and a method for manufacturing the optical semiconductor device are provided.

  A limited object of the present invention is to provide a lens material for an optical semiconductor device that can be ejected using a dispenser and can form a lens having a good lens shape even when ejected by the dispenser, and the lens material for an optical semiconductor device. It is to provide an optical semiconductor device used and a method for manufacturing the optical semiconductor device.

  According to a wide aspect of the present invention, there is provided a liquid lens material used for forming a lens in an optical semiconductor device, represented by the following formula (1) and bonded to a silicon atom with an alkenyl group and a silicon atom. A first organopolysiloxane having a bonded aryl group (excluding an organopolysiloxane having a hydrogen atom bonded to a silicon atom), a hydrogen atom represented by the following formula (51) and bonded to a silicon atom; A second organopolysiloxane having an aryl group bonded to a silicon atom, a hydrosilylation reaction catalyst, and silicon oxide particles, wherein the following formula (1) in the first organopolysiloxane and the second organopolysiloxane: The content ratio of the aryl group bonded to the silicon atom determined by X) is 3 mol% or more and 40 mol% or less, respectively. Lens material for an optical semiconductor device is provided.

  In the above formula (1), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one alkenyl group, at least one represents an aryl group, and R1 to R6 other than the alkenyl group and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

  In the above formula (51), p, q and r are p / (p + q + r) = 0 to 0.50, q / (p + q + r) = 0.40 to 1.0 and r / (p + q + r) = 0 to 0. 50, R51 to R56 represent at least one silicon atom, at least one represents an aryl group, and R51 to R56 other than the silicon atom and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

  Content ratio (mol%) of aryl groups bonded to silicon atoms = (average number of aryl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × aryl) Molecular weight of group / Number average molecular weight of the first organopolysiloxane or the second organopolysiloxane) × 100 Formula (X)

  In the lens material for an optical semiconductor device according to the present invention, the viscosity at 10 rpm at 25 ° C. measured using an E-type viscometer is 1000 mPa · s to 100,000 mPa · s, and the E-type viscometer is used. 4. The ratio of the viscosity at 1 rpm at 25 ° C. measured to the viscosity at 10 rpm at 25 ° C. measured using an E-type viscometer (viscosity at 1 rpm / 10 viscosity at 10 rpm) is 1.5 or more. It is preferably 0 or less.

  The silicon oxide particles are preferably surface-treated with an organosilicon compound. The organosilicon compound is preferably at least one selected from the group consisting of an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon compound having a polydimethylsiloxane group.

  The second organopolysiloxane preferably has a structural unit represented by the following formula (51-a).

  In said formula (51-a), R52 and R53 represent a hydrogen atom, an aryl group, or a C1-C8 hydrocarbon group, respectively.

  The second organopolysiloxane preferably has a vinyl group bonded to a silicon atom.

  The lens material for an optical semiconductor device according to the present invention is preferably a lens material for an optical semiconductor device that is directly discharged using a dispenser onto the surface of a sealing agent that seals the optical semiconductor element.

  An optical semiconductor device according to the present invention includes an optical semiconductor element and a lens formed of a lens material for an optical semiconductor device configured according to the present invention.

  On the specific situation with the optical semiconductor device which concerns on this invention, the sealing agent which has sealed the said optical semiconductor element is further provided, and the said lens is arrange | positioned on the surface of the said sealing agent. .

  In the method of manufacturing an optical semiconductor device according to the present invention, the lens material for an optical semiconductor device configured according to the present invention is formed on the surface of a sealant provided so as to seal the optical semiconductor element using a dispenser. By directly discharging, a lens is formed on the surface of the sealant.

  The lens material for an optical semiconductor device according to the present invention is a first organopolysiloxane represented by formula (1) and having an alkenyl group bonded to a silicon atom and an aryl group bonded to a silicon atom (provided that And a second organopolysiloxane represented by formula (51) having a hydrogen atom bonded to a silicon atom and an aryl group bonded to the silicon atom, and hydrosilylation Since the content ratio of the aryl group bonded to the silicon atom in the first and second organopolysiloxanes is 3 mol% or more and 40 mol% or less, each of which contains a reaction catalyst and silicon oxide particles. Lens-shaped lenses can be formed. Furthermore, the transparency of the lens using the optical semiconductor device lens material according to the present invention can be increased, and the light extracted from the optical semiconductor device having the lens can be brightened.

FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention. FIG. 2 is a front sectional view showing an optical semiconductor device according to another embodiment of the present invention. FIG. 3 is a front sectional view for explaining a lens using a conventional lens material for an optical semiconductor device.

  Details of the present invention will be described below.

  The lens material for optical semiconductor devices according to the present invention is a liquid lens material used for forming a lens in an optical semiconductor device. The lens material for optical semiconductor devices according to the present invention includes a first organopolysiloxane, a second organopolysiloxane, a hydrosilylation catalyst, and silicon oxide particles.

  The first organopolysiloxane (excluding organopolysiloxane having a hydrogen atom bonded to a silicon atom) has an alkenyl group bonded to a silicon atom and an aryl group bonded to a silicon atom. The second organopolysiloxane has a hydrogen atom bonded to a silicon atom and an aryl group bonded to the silicon atom.

  In the present invention, the content ratio of the aryl group bonded to the silicon atom determined by the following formula (X) in the first organopolysiloxane and the second organopolysiloxane is 3 mol% or more and 40 mol% or less, respectively. It is.

  Content ratio (mol%) of aryl groups bonded to silicon atoms = (average number of aryl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × aryl) Molecular weight of group / Number average molecular weight of the first organopolysiloxane or the second organopolysiloxane) × 100 Formula (X)

  A specific first and second organopolysiloxane, a hydrosilylation catalyst and silicon oxide particles, and the content ratio of the aryl group in the first and second organopolysiloxane is 3 mol% or more and 40 mol By adopting a composition that is not more than%, the lens shape can be improved when the lens is formed using the lens material for an optical semiconductor device according to the present invention in the optical semiconductor device. In addition, when a plurality of optical semiconductor devices are manufactured, variation in brightness of light emitted from the obtained plurality of optical semiconductor devices can be reduced. In particular, the use of silicon oxide particles greatly contributes to improving the dispensing property of the lens material and the lens shape. Moreover, by adopting the above composition, the transparency of the lens can be increased, and the brightness of the light extracted from the optical semiconductor device having the lens can be increased.

  The lens material for an optical semiconductor device according to the present invention is preferably a lens material for an optical semiconductor device that is discharged using a dispenser. The lens material for optical semiconductor devices according to the present invention can be discharged using a dispenser. When the lens material for optical semiconductor devices according to the present invention is discharged by a dispenser, a lens having a good lens shape can be easily formed. For this reason, the manufacturing efficiency of the optical semiconductor device is increased.

  Furthermore, the lens material for an optical semiconductor device according to the present invention is directly discharged onto the surface of the optical semiconductor element using a dispenser, or on the surface of a sealant that seals the optical semiconductor element, It is preferably a lens material for an optical semiconductor device that is directly discharged using a dispenser. The lens material for an optical semiconductor device according to the present invention is more preferably a lens material for an optical semiconductor device that is directly discharged using a dispenser onto the surface of a sealant that seals an optical semiconductor element. In this case, the contact between the optical semiconductor element and the corrosive gas in the atmosphere can be effectively suppressed by the sealant and the lens, and an optical semiconductor device having a lens with a good lens shape can be manufactured more efficiently. it can.

(First organopolysiloxane)
The first organopolysiloxane (excluding organopolysiloxane having a hydrogen atom bonded to a silicon atom) contained in the lens material for an optical semiconductor device according to the present invention is represented by the following formula (1): It has an alkenyl group bonded to a silicon atom and an aryl group bonded to a silicon atom. The first organopolysiloxane is a first organopolysiloxane that does not have a hydrogen atom bonded to a silicon atom and has an alkenyl group bonded to a silicon atom and an aryl group bonded to a silicon atom. The first organopolysiloxane is different from the second organopolysiloxane because it does not have hydrogen atoms bonded to silicon atoms. The alkenyl group and aryl group are each directly bonded to a silicon atom. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned. By using this specific first organopolysiloxane, a lens having excellent gas barrier properties can be obtained. As for said 1st organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

In the above formula (1), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one alkenyl group, at least one represents an aryl group, and R1 to R6 other than the alkenyl group and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms. . In the above formula (1), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) each may have an alkoxy group, You may have.

  The above formula (1) shows an average composition formula. The hydrocarbon group in the above formula (1) may be linear or branched. R1 to R6 in the above formula (1) may be the same or different.

In the above formula (1), the oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R6SiO _3/2 ) each form a siloxane bond. An oxygen atom part, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  In general, in each structural unit of the above formula (1), the content of alkoxy groups is small, and the content of hydroxy groups is also small. Generally, when an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed to obtain a first organopolysiloxane, most of the alkoxy groups and hydroxy groups are converted into a partial skeleton of siloxane bonds. It is to be done. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond. When each structural unit of the above formula (1) has an alkoxy group or a hydroxy group, it indicates that a slight amount of unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains. The same applies to the case where each structural unit of formula (51) described later has an alkoxy group or a hydroxy group.

  In the above formula (1), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing the gas barrier property of the lens, the alkenyl group in the first organopolysiloxane and the alkenyl group in the above formula (1) are preferably vinyl groups or allyl groups, and are preferably vinyl groups. More preferred.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (1), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, Examples thereof include n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group and cyclohexyl group.

In the above formula (1), the structural unit represented by (R1R2R3SiO _1/2 ) is a structure in which R1 represents an alkenyl group, and R2 and R3 represent an alkenyl group, an aryl group, or a hydrocarbon group having 1 to 8 carbon atoms. Preferably it contains units. That is, in the above formula (1), the structural unit represented by (R1R2R3SiO _1/2 ) preferably includes a structural unit represented by the following formula (1-a). The structural unit represented by (R1R2R3SiO _1/2 ) may contain only the structural unit represented by the following formula (1-a), and the structural unit represented by the following formula (1-a) and It may contain a structural unit other than the structural unit represented by the formula (1-a). In the structural unit represented by the following formula (1-a), the terminal oxygen atom forms a siloxane bond with the adjacent silicon atom, and shares the oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O _1/2 ”.

  In said formula (1-a), R1 represents an alkenyl group, R2 and R3 represent an alkenyl group, an aryl group, or a C1-C8 hydrocarbon group, respectively. R2 and R3 each preferably represent an aryl group or a hydrocarbon group having 1 to 8 carbon atoms.

From the viewpoint of further suppressing the stickiness of the lens surface, the structural unit represented by (R1R2R3SiO _1/2 ) in 100 mol% of all structural units in the above formula (1), wherein R1 represents an alkenyl group. The ratio of the structural unit (the structural unit represented by the above formula (1-a)) in which R2 and R3 represent an alkenyl group or a hydrocarbon group having 1 to 8 carbon atoms is preferably 5 mol% or more, preferably It is 50 mol% or less, More preferably, it is 45 mol% or less, More preferably, it is 40 mol% or less.

  In the first organopolysiloxane represented by the above formula (1), the content ratio of the aryl group bonded to the silicon atom determined from the following formula (X1) is 3 mol% or more and 40 mol% or less. When the content ratio of the aryl group is 3 mol% or more and 40 mol% or less, the transparency is increased. From the viewpoint of further enhancing the transparency and enhancing the gas barrier property of the lens, the content ratio of the aryl group bonded to the silicon atom is preferably 5 mol% or more. From the viewpoint of further improving the transparency, the content ratio of the aryl group bonded to the silicon atom is preferably 35 mol% or less.

  Content ratio (mol%) of aryl group bonded to silicon atom = (of aryl group bonded to silicon atom contained in one molecule of the first organopolysiloxane whose average composition formula is represented by the above formula (1) Average number × Molecular weight of aryl group / Number average molecular weight of first organopolysiloxane whose average composition formula is represented by the above formula (1)) × 100 Formula (X1)

  When the aryl group in the above formula (X1) is a phenyl group, the content ratio of the aryl group indicates the content ratio of the phenyl group.

In the first organopolysiloxane represented by the above formula (1), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (1-2). Or a structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group.

(R4R5SiXO _1/2 ) (Formula (1-2))

The structural unit represented by (R4R5SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO _2/2 ). Specifically, when the alkoxy group is converted into a partial skeleton of a siloxane bond, the structural unit represented by (R4R5SiO _2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown. When an unreacted alkoxy group remains, or when the alkoxy group is converted to a hydroxy group, the structural unit represented by (R4R5SiO _2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: The part enclosed with the broken line of the structural unit represented by (1-2-b) is shown.

  In the above formulas (1-2) and (1-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in the above formulas (1-b), (1-2) and (1-2b) are the same groups as R4 and R5 in the above formula (1).

In the first organopolysiloxane represented by the above formula (1), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (1-3) or ( 1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a silicon atom in a trifunctional structural unit. One of the bonded oxygen atoms may contain a structure constituting a hydroxy group or an alkoxy group.

(R6SiX ₂ O _1/2 ) Formula (1-3)
(R6SiXO _2/2 ) Formula (1-4)

The structural unit represented by (R6SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or (1 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO _3/2 ).

  In the above formulas (1-3), (1-3-c), (1-4) and (1-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formulas (1-c), (1-3), (1-3-c), (1-4) and (1-4-c) is the same as R6 in the above formula (1). It is the basis of.

  The above formulas (1-b) and (1-c), formulas (1-2) to (1-4), and formulas (1-2b), (1-3-c) and (1-4- In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

In the above formula (1), a / (a + b + c) is 0 or more and 0.50 or less. When a / (a + b + c) is less than or equal to the above upper limit, the heat resistance of the lens is further increased, and lens peeling can be further suppressed. In said formula (1), a / (a + b + c) becomes like this. Preferably it is 0.45 or less, More preferably, it is 0.40 or less. When a is 0 and a / (a + b + c) is 0, there is no structural unit of (R1R2R3SiO _1/2 ) in the above formula (1).

In said formula (1), b / (a + b + c) is 0.40 or more and 1.0 or less. When b / (a + b + c) is not less than the above lower limit, the lens does not become too hard and cracks are hardly generated in the lens. When b (a + b + c) is not more than the above upper limit and the structural unit of (R4R5SiO _2/2 ) exists, the gas barrier property of the lens is further enhanced. In the above formula (1), b / (a + b + c) is preferably 0.50 or more.

In the above formula (1), c / (a + b + c) is 0 or more and 0.50 or less. When c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity as a lens material, and the adhesion of the lens is further enhanced. In said formula (1), c / (a + b + c) becomes like this. Preferably it is 0.45 or less, More preferably, it is 0.40 or less, More preferably, it is 0.35 or less. In addition, when c is 0 and c / (a + b + c) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1).

  C / (a + b + c) in the above formula (1) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1) is preferably the first organopolysiloxane represented by the following formula (1A). As a result, cracks are less likely to occur in the lens, and the lens is more difficult to peel from the sealant or the like.

  In the above formula (1A), a and b satisfy a / (a + b) = 0 to 0.50 and b / (a + b) = 0.50 to 1.0, and at least one of R1 to R5 is alkenyl Group, at least one represents an aryl group, and R1 to R6 other than the alkenyl group and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms.

  In said formula (1A), a / (a + b) becomes like this. Preferably it is 0.45 or less, More preferably, it is 0.40 or less. In the above formula (1A), b / (a + b) is preferably 0.55 or more, more preferably 0.60 or more.

When the first organopolysiloxane was subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation was observed depending on the type of substituent, The peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) in formula (1) appears in the vicinity of +10 to −5 ppm, and (R4R5SiO _2/2 ) and (1-2) in formula (1) above. Each peak corresponding to the bifunctional structural unit of appears in the vicinity of −10 to −50 ppm, (R6SiO _3/2 ) in the above formula (1), and the trifunctional structure of (1-3) and (1-4) Each peak corresponding to the unit appears in the vicinity of −50 to −80 ppm.

Therefore, ²⁹ Si-NMR is measured, and the ratio of each structural unit in the above formula (1) can be measured by comparing the peak areas of the respective signals.

However, in the case where the structural unit in the above formula (1) cannot be identified by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also the ¹ H-NMR measurement result. Can be used to distinguish the proportion of each structural unit in the above formula (1).

(Second organopolysiloxane)
The second organopolysiloxane contained in the lens material for an optical semiconductor device according to the present invention is represented by the following formula (51), and includes a hydrogen atom bonded to a silicon atom and an aryl group bonded to the silicon atom. Have. Each of the hydrogen atom and the aryl group is directly bonded to the silicon atom. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group. By using this specific second organopolysiloxane, a lens having excellent gas barrier properties can be obtained. As for the said 2nd organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

In the above formula (51), p, q and r are p / (p + q + r) = 0 to 0.50, q / (p + q + r) = 0.40 to 1.0 and r / (p + q + r) = 0 to 0. 50, R51 to R56 represent at least one silicon atom, at least one represents an aryl group, and R51 to R56 other than the silicon atom and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms. . In the above formula (51), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

  The above formula (51) represents an average composition formula. The hydrocarbon group in the above formula (51) may be linear or branched. R51 to R56 in the above formula (51) may be the same or different.

In the above formula (51), the oxygen atom part in the structural unit represented by (R54R55SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R56SiO _3/2 ) each form a siloxane bond. An oxygen atom part, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (51), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, vinyl group and allyl group Is mentioned.

From the viewpoint of enhancing the curability of the lens material and further suppressing cracking and peeling in the thermal cycle, the structural unit represented by (R51R52R53SiO _1/2 ) in the above formula (51) is such that R51 represents a hydrogen atom. It is preferable that R52 and R53 include a structural unit representing a hydrogen atom, an aryl group, or a hydrocarbon group having 1 to 8 carbon atoms. The structural unit represented by (R51R52R53SiO1 _{/ 2} ) in the above formula (51) includes a structural unit in which R51 represents a hydrogen atom, and R52 and R53 represent an aryl group or a hydrocarbon group having 1 to 8 carbon atoms. It is more preferable.

That is, in the above formula (51), the structural unit represented by (R51R52R53SiO _1/2 ) preferably includes a structural unit represented by the following formula (51-a). The structural unit represented by (R51R52R53SiO _1/2 ) may include only the structural unit represented by the following formula (51-a), and the structural unit represented by the following formula (51-a) and the following And a structural unit other than the structural unit represented by Formula (51-a).

  In said formula (51-a), R52 and R53 represent a hydrogen atom, an aryl group, or a C1-C8 hydrocarbon group, respectively. R52 and R53 each preferably represent an aryl group or a hydrocarbon group having 1 to 8 carbon atoms.

From the viewpoint of enhancing the curability of the lens material and further suppressing cracking and peeling during thermal cycling, the structure represented by (R51R52R53SiO _1/2 ) in 100 mol% of all structural units in the above formula (51). A structural unit (R51 represents a hydrogen atom, R52 and R53 represent a hydrogen atom, an aryl group, or a hydrocarbon group having 1 to 8 carbon atoms (a structural unit represented by the above formula (51-a)). The ratio is preferably 5 mol% or more, more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 45 mol% or less.

  From the viewpoint of further improving the curability of the lens, the second organopolysiloxane preferably has a vinyl group bonded to a silicon atom. In this case, at least one of R51 to R56 represents a silicon atom, at least one represents an aryl group, at least one represents a vinyl group, and R51 to R56 other than a hydrogen atom, an aryl group, and a vinyl group. Represents a hydrocarbon group having 1 to 8 carbon atoms.

  In the second organopolysiloxane represented by the above formula (51), the content ratio of the aryl group bonded to the silicon atom determined from the following formula (X51) is 3 mol% or more and 40 mol% or less. When the content ratio of the aryl group is 3 mol% or more and 40 mol% or less, the transparency is increased. From the viewpoint of further enhancing the transparency and enhancing the gas barrier property of the lens, the content ratio of the aryl group bonded to the silicon atom is preferably 5 mol% or more. From the viewpoint of further improving the transparency, the content ratio of the aryl group bonded to the silicon atom is preferably 35 mol% or less.

Content ratio (mol%) of aryl group bonded to silicon atom = (of aryl group bonded to silicon atom contained in one molecule of second organopolysiloxane whose average composition formula is represented by the above formula (51)) Average number × Molecular weight of aryl group / Number average molecular weight of second organopolysiloxane whose average composition formula is represented by the above formula (51)) × 100 Formula (X51)
When the aryl group in the above formula (X51) is a phenyl group, the content ratio of the aryl group indicates the content ratio of the phenyl group.

In the second organopolysiloxane represented by the above formula (51), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (51-2). Or a structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group.

(R54R55SiXO _1/2 ) Formula (51-2)

The structural unit represented by (R54R55SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO _2/2 ).

  In the above formulas (51-2) and (51-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R54 and R55 in the above formulas (51-b), (51-2) and (51-2-b) are the same groups as R54 and R55 in the above formula (51).

In the second organopolysiloxane represented by the above formula (51), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (51-3) or ( 51-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a silicon atom in a trifunctional structural unit. One of the bonded oxygen atoms may contain a structure constituting a hydroxy group or an alkoxy group.

(R56SiX ₂ O _1/2 ) (Formula (51-3)
(R56SiXO _2/2 ) Formula (51-4)

The structural unit represented by (R56SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or (51 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO _3/2 ).

  In the above formulas (51-3), (51-3-c), (51-4) and (51-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formulas (51-c), (51-3), (51-3-c), (51-4) and (51-4-c) is the same as R56 in the above formula (51). It is the basis of.

  The above formulas (51-b) and (51-c), formulas (51-2) to (51-4), and formulas (51-2-b), (51-3-c) and (51-4-) In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

In the above formula (51), p / (p + q + r) is 0 or more and 0.50 or less. When p / (p + q + r) is less than or equal to the above upper limit, the heat resistance of the lens is further increased, and lens peeling can be further suppressed. In said formula (51), p / (p + q + r) becomes like this. Preferably it is 0.10 or more, More preferably, it is 0.45 or less. When p is 0 and p / (p + q + r) is 0, there is no structural unit (R51R52R53SiO _1/2 ) in the above formula (51).

In said formula (51), q / (p + q + r) is 0.40 or more and 1.0 or less. When q / (p + q + r) is not less than the above lower limit, the lens does not become too hard and cracks are hardly generated in the lens. When q / (p + q + r) is not more than the above upper limit and the structural unit of (R54R55SiO _2/2 ) exists, the gas barrier property of the lens is further enhanced. In said formula (51), q / (p + q + r) becomes like this. Preferably it is 0.5 or more, More preferably, it is 0.95 or less.

In the above formula (51), r / (p + q + r) is 0 or more and 0.50 or less. The larger r / (p + q + r) is, the higher the hardness of the lens is, and it is possible to prevent scratches and dust from being attached, the heat resistance of the lens is increased, and the thickness of the lens tends to be less likely to decrease under a high temperature environment. When r / (p + q + r) is less than or equal to the above upper limit, it is easy to maintain an appropriate viscosity as a lens material, and the adhesion of the lens can be further enhanced. When r is 0 and r / (p + q + r) is 0, there is no structural unit (R56SiO _3/2 ) in the above formula (51).

When the second organopolysiloxane was subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation was observed depending on the type of substituent, The peak corresponding to the structural unit represented by (R51R52R53SiO _1/2 ) in formula (51) appears in the vicinity of +10 to −5 ppm, and (R54R55SiO _2/2 ) and (51-2) in formula (51) above. Each peak corresponding to the bifunctional structural unit of appears in the vicinity of −10 to −50 ppm, (R56SiO _3/2 ) in the above formula (51), and the trifunctional structure of (51-3) and (51-4) Each peak corresponding to the unit appears in the vicinity of −50 to −80 ppm.

Therefore, the ratio of each structural unit in the above formula (51) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the formula (51) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also the ¹ H-NMR measurement result Can be used to distinguish the ratio of each structural unit in the above formula (51).

  The content of the second organopolysiloxane is preferably 10 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the first organopolysiloxane. When the contents of the first and second organopolysiloxanes are within this range, a lens having a better gas barrier property can be obtained. From the viewpoint of obtaining a lens having an even better gas barrier property, the content of the second organopolysiloxane is more preferably 30 parts by weight or more, still more preferably with respect to 100 parts by weight of the first organopolysiloxane. Is 50 parts by weight or more, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less.

(Other properties of the first and second organopolysiloxanes and synthesis methods thereof)
The alkoxy group content of the first and second organopolysiloxanes is preferably 0.5 mol% or more, more preferably 1 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. is there. When the content of the alkoxy group is not less than the above lower limit, the adhesion of the lens becomes high. When the alkoxy group content is not more than the above upper limit, the storage stability of the first and second organopolysiloxanes and the lens material is increased, and the heat resistance of the lens is further increased.

  The content of the alkoxy group means the amount of the alkoxy group contained in the average composition formula of the first and second organopolysiloxanes.

  The first and second organopolysiloxanes preferably do not contain silanol groups. When the first and second organopolysiloxanes do not contain silanol groups, the storage stability of the first and second organopolysiloxanes and the lens material is increased. The amount of silanol groups can be reduced by heating under vacuum. The content of silanol groups can be measured using infrared spectroscopy.

  The number average molecular weight (Mn) of the first and second organopolysiloxanes is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, preferably 50000 or less, more preferably 15000 or less. When the number average molecular weight is not less than the above lower limit, the volatile components are reduced during thermosetting, and the thickness of the lens is difficult to decrease under a high temperature environment. When the number average molecular weight is not more than the above upper limit, the viscosity of the lens material can be easily adjusted.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the first and second organopolysiloxanes is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Among these, from the viewpoint of controlling the reaction, a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction is preferable.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method of reacting the alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing an aryl group into the first and second organopolysiloxanes include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, And phenyltrimethoxysilane.

  Examples of the organosilicon compound for introducing an alkenyl group into the first organopolysiloxane include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3-divinyl. -1,1,3,3-tetramethyldisiloxane and the like.

  Examples of the organosilicon compound for introducing hydrogen atoms directly bonded to silicon atoms into the second organopolysiloxane include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3. , 3-tetramethyldisiloxane and the like.

  Examples of other organosilicon compounds that can be used to obtain the first and second organopolysiloxanes include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and isopropyl (methyl) dimethoxy. Examples include silane, cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

  Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid. Is mentioned.

  Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.

  Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound. Of these, a potassium-based catalyst or a cesium-based catalyst is preferable.

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the optical semiconductor device lens material according to the present invention includes an alkenyl group bonded to a silicon atom in the first organopolysiloxane and a silicon in the second organopolysiloxane. It is a catalyst that causes a hydrosilylation reaction between a hydrogen atom bonded to an atom.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. A platinum-based catalyst is preferred because the transparency of the lens is increased.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  In order to improve the stability of the platinum-alkenylsiloxane complex and the platinum-olefin complex, it is preferable to add alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin to the platinum-alkenylsiloxane complex or platinum-olefin complex. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  The hydrosilylation reaction catalyst preferably contains a platinum alkenyl complex. The platinum catalyst is preferably a mixture of a platinum alkenyl complex and a phosphorus compound. That is, the platinum catalyst preferably contains a platinum alkenyl complex and a phosphorus compound. As for the said platinum alkenyl complex, only 1 type may be used and 2 or more types may be used together.

  The combined use of the specific first and second organopolysiloxanes with a platinum-based catalyst that is a mixture of a platinum alkenyl complex and a phosphorus compound further increases the gas barrier properties of the lens. Furthermore, cracks are less likely to occur in the cured lens, and the lens is less likely to peel from the sealant or the like.

  Further, the conventional lens material for optical semiconductor devices has a problem that the lens is discolored in a reflow process when mounted on a printed circuit board or the like, and the luminous intensity is lowered. On the other hand, even if it is exposed to severe conditions such as a reflow process by using the specific first and second organopolysiloxanes and a platinum-based catalyst that is a mixture of a platinum alkenyl complex and a phosphorus compound, The lens is difficult to discolor. In addition, the transparency of the lens can be increased by using a platinum-based catalyst that is a mixture of a platinum alkenyl complex and a phosphorus compound.

  Examples of the phosphorus compound include triphenylphosphine, tricyclohexylphosphine, and triethylphosphine. From the viewpoint of obtaining a lens that is more difficult to discolor even when exposed to harsh conditions, the phosphorus compound is preferably triphenylphosphine.

  In the lens material, the content of the catalyst for hydrosilylation reaction is preferably 0.01 ppm or more and 1000 ppm or less in terms of the weight unit of metal atom (or platinum element when the metal atom is platinum element). When the content of the catalyst for hydrosilylation reaction is 0.01 ppm or more, it is easy to sufficiently cure the lens material, and the gas barrier property of the lens can be further enhanced. When the content of the catalyst for hydrosilylation reaction is 1000 ppm or less, the problem of lens coloring hardly occurs. The content of the hydrosilylation catalyst in the lens material is more preferably 1 ppm or more, and more preferably 500 ppm or less, in terms of weight units of metal atoms.

  In the case of using a platinum-based catalyst that is a mixture of a platinum alkenyl complex and a phosphorus compound, the platinum-based catalyst is 0.1: 99.9 to 99.9: by weight ratio of platinum element and the phosphorus compound. It is preferable to include by 0.1, and it is more preferable to include by 1: 99-20: 80.

(Silicon oxide particles)
The lens material for an optical semiconductor device according to the present invention further includes silicon oxide particles. By using the silicon oxide particles, the viscosity of the lens material before curing can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the cured lens. Therefore, the handleability of the lens material can be improved.

  The primary particle diameter of the silicon oxide particles is preferably 5 nm or more, more preferably 8 nm or more, preferably 200 nm or less, more preferably 150 nm or less. When the primary particle diameter of the silicon oxide particles is not less than the above lower limit, the dispersibility of the silicon oxide particles is further increased, and the transparency of the lens is further increased. When the primary particle diameter of the silicon oxide particles is not more than the above upper limit, it is possible to sufficiently obtain the effect of increasing the viscosity at 25 ° C. and to suppress the decrease in the viscosity due to the temperature increase.

  The primary particle diameter of the silicon oxide particles is measured as follows. The cured product of the lens material for an optical semiconductor device is observed using a transmission electron microscope (trade name “JEM-2100”, manufactured by JEOL Ltd.). The size of the primary particles of 100 silicon oxide particles in the visual field is measured, and the average value of the measured values is defined as the primary particle diameter. The primary particle diameter means an average value of the diameters of the silicon oxide particles when the silicon oxide particles are spherical, and an average value of the major diameters of the silicon oxide particles when the silicon oxide particles are non-spherical.

The BET specific surface area of the silicon oxide particles is preferably 30 m ² / g or more, and preferably 400 m ² / g or less. When the BET specific surface area is not less than the above lower limit, the viscosity of the lens material at 25 ° C. can be controlled within a suitable range, and the decrease in the viscosity due to the temperature rise can be suppressed. When the BET specific surface area is less than or equal to the above upper limit, the aggregation of silicon oxide particles is less likely to occur, the dispersibility of the silicon oxide particles is further increased, and the transparency of the lens is further increased.

  The silicon oxide particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, and silica produced by a wet method such as colloidal silica, sol-gel silica and precipitated silica. It is done. Among these, fumed silica is suitably used as the silicon oxide particles from the viewpoint of obtaining a lens having less volatile components and higher transparency.

Examples of the fumed silica include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 (specific surface area). : 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  The silicon oxide particles are preferably surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and it is possible to further suppress the decrease in the viscosity due to the temperature increase of the lens material before curing.

  The organosilicon compound is not particularly limited. For example, a silane compound having an alkyl group, a silicon compound having a siloxane skeleton such as dimethylsiloxane, a silicon compound having an amino group, and a silicon compound having a (meth) acryloyl group. Examples thereof include a compound and a silicon compound having an epoxy group. The “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.

  From the viewpoint of further enhancing dispersibility of the silicon oxide particles, the organosilicon compound is selected from the group consisting of an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon compound having a polydimethylsiloxane group. It is preferable that at least one selected. Further, from the viewpoint of further enhancing dispersibility of the silicon oxide particles, the organosilicon compound used for the surface treatment is at least one of an organosilicon compound having a trimethylsilyl group and an organosilicon compound having a polydimethylsiloxane group. It is preferable that

  When a lens material containing an aryl group-containing first and second organopolysiloxane and a phosphor is exposed to a high temperature before curing, the viscosity of the lens material is drastically lowered and the phosphor is likely to settle. For this reason, when the lens material is exposed to a high temperature during curing, the phosphor is unevenly distributed and the light is irregularly reflected. As a result, there is a problem that a part of the light emitted from the light emitting element is lost in the lens, and the amount of light extracted from the optical semiconductor device is reduced.

  Although the lens material for an optical semiconductor device according to the present invention includes the first and second organopolysiloxane having an aryl group by including the silicon oxide particles surface-treated with the organosilicon compound, The viscosity of the lens material at a high temperature can be maintained at a sufficiently high level. Thereby, the viscosity when the lens material is heated to a high temperature can be adjusted to an appropriate range, and the dispersion state of the phosphor in the lens material can be kept uniform.

  As an example of a method for surface treatment with an organosilicon compound, when using an organosilicon compound having a dimethylsilyl group or an organosilicon compound having a trimethylsilyl group, for example, dichlorodimethylsilane, dimethyldimethoxysilane, hexamethyldisilazane, A method of surface-treating silicon oxide particles using trimethylsilyl chloride, trimethylmethoxysilane, or the like can be given. In the case of using an organosilicon compound having a polydimethylsiloxane group, a method of surface-treating silicon oxide particles using a compound having a silanol group at the terminal of the polydimethylsiloxane group, cyclic siloxane, or the like can be mentioned.

Examples of commercially available silicon oxide particles surface-treated with the above organosilicon compound having a dimethylsilyl group include R974 (specific surface area: 170 m ² / g) and R964 (specific surface area: 250 m ² / g) (both Nippon Aerosil Etc.).

Commercially available silicon oxide particles surface-treated with the above organosilicon compound having a trimethylsilyl group include RX200 (specific surface area: 140 m ² / g) and R8200 (specific surface area: 140 m ² / g) (both from Nippon Aerosil Co., Ltd.) Manufactured) and the like.

RY200 (specific surface area: 120 m ² / g) (manufactured by Nippon Aerosil Co., Ltd.) and the like can be mentioned as a commercial product of silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group.

  The method for surface-treating the silicon oxide particles with the organosilicon compound is not particularly limited. As this method, for example, a dry method in which silicon oxide particles are added to a mixer and an organosilicon compound is added while stirring, a slurry method in which an organosilicon compound is added to a slurry of silicon oxide particles, and silicon oxide particles And a direct treatment method such as a spray method in which an organosilicon compound is sprayed after drying. Examples of the mixer used in the dry method include a Henschel mixer and a V-type mixer. In the dry method, the organosilicon compound is added directly or as an alcohol aqueous solution, an organic solvent solution or an aqueous solution.

  In preparing a lens material for an optical semiconductor device in order to obtain silicon oxide particles surface-treated with the organosilicon compound, the silicon oxide particles and the matrix resin such as the first and second organopolysiloxane are used. An integral blend method in which an organosilicon compound is directly added during mixing may be used.

  The content of the silicon oxide particles is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the total of the first organopolysiloxane and the second organopolysiloxane. The amount is preferably 40 parts by weight or less, more preferably 35 parts by weight or less. When the content of the silicon oxide particles is equal to or higher than the lower limit, it is possible to suppress a decrease in viscosity at the time of curing. When the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the lens material can be controlled to a more appropriate range, and the transparency of the lens can be further enhanced.

(Phosphor)
The lens material for optical semiconductor devices according to the present invention may further contain a phosphor. The phosphor acts so that light of a desired color can be finally obtained by absorbing light when the light emitted from the light emitting element reaches the lens and generating fluorescence. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color can be obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.

  For example, when it is intended to finally obtain white light using an ultraviolet LED chip as a light emitting element, it is preferable to use a combination of a blue phosphor, a red phosphor and a green phosphor. When it is intended to finally obtain white light using a blue LED chip as a light emitting element, it is preferable to use a combination of a green phosphor and a red phosphor, or a yellow phosphor. As for the said fluorescent substance, only 1 type may be used and 2 or more types may be used together.

The blue phosphor is not particularly limited. For example, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu and the like.

It is not particularly restricted but includes the red phosphor, for _{example, (Sr, Ca) S:} Eu, (Ca, Sr) 2 Si 5 N 8: Eu, CaSiN 2: Eu, CaAlSiN 3: Eu, Y 2 O 2 S : Eu, La ₂ O ₂ S: Eu, LiW ₂ O ₈ : (Eu, Sm), (Sr, Ca, Bs, Mg) ₁₀ (PO ₄ ) ₈ Cl ₂ : (Eu, Mn), Ba ₃ MgSi ₂ And O ₈ : (Eu, Mn).

The green phosphor is not particularly limited, and for example, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, SrGa ₂ S ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, SrSiON: Eu, ZnS: (Cu, Al), BaMgAl ₁₀ O ₁₇ (Eu, Mn), SrAl ₂ O ₄ : Eu, and the like.

Is not particularly restricted but includes the yellow phosphor, for _{example, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, Tb 3 Al 5 O 12: Ce, CaGa 2 S 4: Eu , Sr ₂ SiO ₄ : Eu, and the like.

  Furthermore, examples of the phosphor include perylene compounds that are organic phosphors.

  The phosphor has a volume average particle size of preferably 1 μm or more, more preferably 2 μm or more, preferably 30 μm or less, more preferably 25 μm or less.

  The phosphor content can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. The phosphor content is preferably 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the lens material for optical semiconductor devices according to the present invention. When the material for an optical semiconductor device according to the present invention includes a phosphor, the content of the phosphor is 0.1 with respect to 100 parts by weight of all components excluding the phosphor of the lens material for an optical semiconductor device. It is preferable that it is not less than 40 parts by weight.

(Other ingredients)
The lens material for an optical semiconductor device according to the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, a heat conductive filler, a flame retardant, etc. An additive may further be included.

  The first organopolysiloxane, the second organopolysiloxane, the hydrosilylation reaction catalyst, and the silicon oxide particles are prepared separately in a liquid containing one or more of these. A lens material for an optical semiconductor device according to the present invention may be prepared by mixing a plurality of liquids immediately before use. For example, the liquid A containing the first organopolysiloxane and the hydrosilylation reaction catalyst and the liquid B containing the second organopolysiloxane are prepared separately, and the liquid A and liquid B immediately before use. May be mixed to prepare the lens material for optical semiconductor devices according to the present invention. As described above, the first organopolysiloxane, the catalyst for hydrosilylation reaction, and the second organopolysiloxane are separately made into two liquids of the first liquid and the second liquid, so that the storage stability is improved. Can be improved. The silicon oxide particles may be added to the A liquid, the B liquid, or the A liquid and the B liquid.

(Details and applications of lens materials for optical semiconductor devices)
The lens material for optical semiconductor devices according to the present invention is liquid. Liquid forms include pastes.

  The viscosity η10 at 10 rpm at 25 ° C. measured using an E-type viscometer of the optical semiconductor device lens material according to the present invention is preferably 1000 mPa · s or more and 100,000 mPa · s or less. In this case, the lens shape formed by the lens material for an optical semiconductor device can be further improved, and the lens material can be discharged with high accuracy by a dispenser. From the viewpoint of further improving the lens shape and further improving the discharge accuracy of the lens material by the dispenser, the viscosity η10 is more preferably 5000 mPa · s or more, and more preferably 50000 mPa · s or less.

  The viscosity η1 at 1 rpm at 25 ° C. measured using the mold viscometer of the lens material for optical semiconductor devices according to the present invention was measured using the mold viscometer of the lens material for optical semiconductor devices according to the present invention. The ratio (η1 / η10) to the viscosity η10 at 10 rpm at 25 ° C. is preferably 1.5 or more and 5.0 or less. In this case, the lens shape formed by the lens material for an optical semiconductor device is further improved. In addition, the lens material can be accurately discharged by the dispenser. The ratio (η1 / η10) is more preferably 1.8 or more, and more preferably 4.0 or less from the viewpoint of further improving the lens shape and further increasing the discharge accuracy of the lens material by the dispenser. .

  From the viewpoint of further improving the lens shape of the lens and further improving the discharge accuracy of the lens material by the dispenser, the viscosity η10 is not less than the lower limit and not more than the upper limit, and the ratio (η1 / η10) is the above. It is preferable that it is not less than the lower limit and not more than the above upper limit.

  The “viscosity” in the lens material for an optical semiconductor device is a value measured using an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.).

  The curing temperature of the optical semiconductor device lens material according to the present invention is not particularly limited. The curing temperature of the lens material for optical semiconductor devices is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the curing temperature is equal to or higher than the above lower limit, the lens material is sufficiently cured. If the curing temperature is not more than the above upper limit, thermal degradation of the lens is unlikely to occur.

  Although it does not specifically limit as a hardening system, It is preferable to use a step cure system. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the lens can be suppressed.

  The method for producing a lens material for an optical semiconductor device according to the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll, or a bead mill, Or the method of mixing the said 1st organopolysiloxane, the said 2nd organopolysiloxane, the said catalyst for hydrosilylation reaction, the silicon oxide particle | grains, and the other component mix | blended as needed, etc. is mentioned under a heating. It is done.

  The light emitting element is not particularly limited as long as it is a light emitting element using a semiconductor. For example, when the light emitting element is a light emitting diode, for example, a structure in which a semiconductor material for LED type is stacked on a substrate can be given. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  An optical semiconductor device according to the present invention includes an optical semiconductor element and a lens formed of the lens material for an optical semiconductor device according to the present invention. The lens is obtained by curing the lens material according to the present invention, and is a cured product of the lens material. The optical semiconductor device according to the present invention preferably further includes a sealing agent that seals the optical semiconductor element. The surface (upper surface) of the sealant is preferably flat. In the optical semiconductor device according to the present invention, the lens is preferably disposed on the surface of the sealant. However, the lens may be disposed on the surface of the optical semiconductor element.

  The lens shape is not particularly limited. From the viewpoint of controlling the light emission direction in the optical semiconductor device and further suppressing the front luminance from becoming too high, the lens shape is preferably a part of a sphere or a part of a spheroid.

  When obtaining the optical semiconductor device, the lens material for the optical semiconductor device is formed on the surface of the optical semiconductor element or on the surface of the sealing agent provided so as to seal the optical semiconductor element using a dispenser. It is preferable to form a lens on the surface of the sealing agent by directly ejecting.

(Embodiment of optical semiconductor device)
FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  An optical semiconductor device 1 shown in FIG. 1 has a housing 2. An optical semiconductor element 3 is arranged and mounted in the housing 2. The optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2. The optical semiconductor element 3 is a light emitting element such as an LED.

  The inner surface 2a is formed so that the diameter of the inner surface 2a increases toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3. A sealing agent 4 is filled in a region surrounded by the inner surface 2 a so as to seal the optical semiconductor element 3. That is, the optical semiconductor element 3 is sealed with the sealant 4 in the housing 2. In the optical semiconductor device 1, a cured product of the sealant 4 is disposed so as to seal the optical semiconductor element 3.

  Furthermore, in the optical semiconductor device 1, the lens 5 is disposed on the surface 4 a of the sealant 4.

  FIG. 2 is a front sectional view showing an optical semiconductor device according to another embodiment of the present invention.

  In the optical semiconductor device 11 shown in FIG. 2, an optical semiconductor element 13 is arranged and mounted on a substrate 12 having terminals 12a provided on the upper surface. An electrode 13 a provided on the upper surface of the optical semiconductor element 13 and a terminal 12 a provided on the upper surface of the substrate 12 are electrically connected by a bonding wire 14. Further, in the optical semiconductor device 11, a lens 15 is disposed on the optical semiconductor element 13. The lens 15 covers the surface of the optical semiconductor element 13 and the bonding wire 14.

  The lenses 5 and 15 are formed by curing the lens material for an optical semiconductor device according to the present invention, and are a cured product of the lens material. Therefore, the lens shapes of the lenses 5 and 15 are good. Further, since the lenses 5 and 15 are highly transparent, the brightness of the light extracted from the optical semiconductor devices 1 and 11 can be increased.

  On the other hand, when a conventional lens material for an optical semiconductor device is ejected by a dispenser to form a lens, an ejection trace 101a from the dispenser may remain on the upper end of the lens 101 as shown in FIG. As shown in FIG. 3B, the lens material may spread laterally, leaving a mark 102a remaining on the lens 102. By using the lens material for an optical semiconductor device according to the present invention, it is possible to effectively suppress the formation of the discharge trace 101a and the wet spread mark 102a.

  The structures shown in FIGS. 1 and 2 are merely examples of the optical semiconductor device according to the present invention, and the mounting structure and the like of the optical semiconductor device can be modified as appropriate.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(Synthesis Example 1) Synthesis of First Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 94 g of trimethylmethoxysilane, 99 g of dimethyldimethoxysilane, 92 g of diphenyldimethoxysilane, and 133 g of vinyltrimethoxysilane And stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 108 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution and heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (A).

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(Me ₃ SiO _1/2 ) _0.29 (Me ₂ SiO _2/2 ) _0.27 (Ph ₂ SiO _2/2 ) _0.13 (ViSiO _3/2 ) _0.31 ... Formula (A1)

  In the above formula (A1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (A) was 21 mol%.

(Synthesis Example 2) Synthesis of the first organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 7.82 g of vinyldimethylethoxysilane, 310 g of dimethyldimethoxysilane and 88 g of diphenyldimethoxysilane were added, Stir at 50 ° C. A solution prepared by dissolving 0.8 g of potassium hydroxide in 142 g of water was slowly added dropwise thereto, and after the addition, the mixture was stirred at 50 ° C. for 6 hours to be reacted to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 0.9 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (B).

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(ViMe ₂ SiO _1/2 ) _0.02 (Me ₂ SiO _2/2 ) _0.85 (Ph ₂ SiO _2/2 ) _0.13 ... Formula (B1)

  In the above formula (B1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The content ratio of the phenyl group of the obtained polymer (B) was 22 mol%.

(Synthesis Example 3) Synthesis of Second Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 31 g of trimethylmethoxysilane, 50 g of 1,1,3,3-hexamethyldisiloxane, dimethyldimethoxy 140 g of silane, 59 g of diphenyldimethoxysilane, 48 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 92 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, it heated under reduced pressure and the volatile component was removed and the polymer was obtained. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (C) was obtained.

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.24 (Me ₂ SiO _2/2 ) _0.38 (Ph ₂ SiO _2/2 ) _0.08 (PhSiO _3/2 ) _0.10 (ViSiO _3/2 ) _0.10 Formula (C1)

  In the above formula (C1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (C) was 23 mol%.

Synthesis Example 4 Synthesis of Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 375 g of dimethyldimethoxysilane, 98 g of diphenyldimethoxysilane, 10.6 g of vinylmethyldimethoxysilane, and methyl Diethoxysilane 54g was added and stirred at 50 ° C. Into this, a solution of 2.1 g of hydrochloric acid and 144 g of water was slowly added dropwise. After the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (D) was obtained.

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (D) had the following average composition formula (D1).

(Me ₂ SiO _2/2 ) _0.77 (Ph ₂ SiO _2/2 ) _0.11 (ViMeSiO _2/2 ) _0.02 (HMeSiO _2/2 ) _0.10 ... Formula (D1)

  In the above formula (D1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (D) was 20 mol%.

(Synthesis Example 5) Synthesis of organopolysiloxane similar to the first organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 476 g of dimethyldimethoxysilane and 5.3 g of vinylmethyldimethoxysilane were added. And stirred at 50 ° C. A solution prepared by dissolving 2.2 g of potassium hydroxide in 144 g of water was slowly added dropwise thereto, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 2.4 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (E).

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (E) had the following average composition formula (E1).

(Me ₂ SiO _2/2 ) _0.99 (ViMeSiO _2/2 ) _0.01 Formula (E1)

  In the above formula (E1), Me represents a methyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (E) was 0 mol%.

Synthesis Example 6 Synthesis of Organopolysiloxane Similar to Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 24 g of 1,1,3,3-tetramethyldisiloxane, And 438 g of dimethyldimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 2.0 g of hydrochloric acid and 134 g of water was slowly added dropwise. After the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, it heated under reduced pressure and the volatile component was removed and the polymer was obtained. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (F) was obtained.

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(HMe ₂ SiO _1/2 ) _0.08 (Me ₂ SiO _2/2 ) _0.92 Formula (F1)

  In the above formula (F1), Me represents a methyl group.

  The content ratio of the phenyl group of the obtained polymer (F) was 0 mol%.

Example 1
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (amount in which platinum metal is 10 ppm by weight with respect to the entire lens material) ), And ² g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), defoaming, A lens material for an optical semiconductor device was obtained.

(Example 2)
Polymer B (16 g), Polymer D (4 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (amount in which platinum metal is 10 ppm by weight with respect to the entire lens material) ) And 2.5 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.) The lens material for optical semiconductor devices was obtained.

(Comparative Example 1)
Polymer E (16 g), Polymer F (4 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (amount of platinum metal in weight unit of 10 ppm with respect to the entire lens material) ) And 2.5 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.) The lens material for optical semiconductor devices was obtained.

(Comparative Example 2)
Polymer E (16 g), Polymer F (4 g), and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire lens material) Amount) was mixed and defoamed to obtain a lens material for an optical semiconductor device.

(Evaluation)
(Measurement of viscosity at 25 ° C.)
Using an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.), the viscosity η1 (mPa · s) at 1 rpm at 25 ° C. of the lens material for optical semiconductor devices was measured. Moreover, the viscosity (eta) 10 (mPa * s) in 10 rpm in 25 degreeC of the obtained lens material for optical semiconductor devices was measured using the E-type viscosity meter (TV-22 type, the Toki Sangyo company make).

(Production of optical semiconductor device)
Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (platinum metal becomes 10 ppm by weight with respect to the whole sealant) Amount), silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), and phosphor powder (volume) 1.0 part by weight of an average particle size of 17 μm, a specific gravity of 4.7, “EY4453”, manufactured by Intematics Co., Ltd.) was mixed and defoamed to prepare an encapsulant for optical semiconductor devices.

  In a structure in which a light emitting element having a main emission peak of 460 nm is mounted on a silver-plated polyphthalamide housing material with a lead electrode by a die bond material, and the light emitting element and the lead electrode are connected by a gold wire. The obtained sealant for optical semiconductor devices was injected and cured by heating at 150 ° C. for 2 hours.

  Next, after the lens material for optical semiconductor devices obtained in Examples and Comparative Examples was directly discharged from a dispenser device (“SHOTMASTER-300” manufactured by Musashi Engineering Co., Ltd.) to the flat surface (upper surface) of the sealant, The lens material was cured by heating at 150 ° C. for 2 hours. In this way, a lens was formed on the surface of the sealant, and an optical semiconductor device was manufactured. Using this optical semiconductor device, the following evaluation items were evaluated.

(Lens shape)
The shape of the lens was confirmed visually. The case where no protrusion or dripping occurred in the lens was determined as “◯”, and the case where protrusion or dripping occurred in the lens was determined as “x”.

(Lens transparency)
The transparency of the lens was confirmed visually. The case where the lens was transparent was determined as “◯”, the case where it was slightly cloudy was determined as “Δ”, and the case where it was cloudy was determined as “x”.

(Brightness evaluation)
A current of 100 mA was applied to each of the light emitting elements in 50 optical semiconductor devices at 23 ° C., and the light intensity was measured using a light intensity measuring device (OL770, manufactured by Optronic Laboratories). The average value of 50 light was 6.0 cd. The above was designated as “◯” and the value less than 6.0 scd was designated as “x”.

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 2a ... Inner surface 3 ... Optical semiconductor element 4 ... Sealing agent 4a ... Surface 5 ... Lens 11 ... Optical semiconductor device 12 ... Substrate 12a ... Terminal 13 ... Optical semiconductor element 13a ... Electrode 14 ... Bonding wire 15 ... Lens

Claims (10)

A liquid lens material used to form a lens in an optical semiconductor device,
A first organopolysiloxane represented by the following formula (1) and having an alkenyl group bonded to a silicon atom and an aryl group bonded to a silicon atom (excluding an organopolysiloxane having a hydrogen atom bonded to a silicon atom) )When,
A second organopolysiloxane represented by the following formula (51) and having a hydrogen atom bonded to a silicon atom and an aryl group bonded to the silicon atom;
A catalyst for hydrosilylation reaction;
Silicon oxide particles,
The content ratio of the aryl group bonded to the silicon atom determined by the following formula (X) in the first organopolysiloxane and the second organopolysiloxane is 3 mol% or more and 40 mol% or less, respectively. Lens material for semiconductor devices.

In the formula (1), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one alkenyl group, at least one represents an aryl group, and R1 to R6 other than the alkenyl group and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

In the formula (51), p, q and r are p / (p + q + r) = 0 to 0.50, q / (p + q + r) = 0.40 to 1.0 and r / (p + q + r) = 0 to 0. 50, R51 to R56 represent at least one silicon atom, at least one represents an aryl group, and R51 to R56 other than the silicon atom and the aryl group represent a hydrocarbon group having 1 to 8 carbon atoms. .
Content ratio (mol%) of aryl groups bonded to silicon atoms = (average number of aryl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × aryl Molecular weight of group / number average molecular weight of the first organopolysiloxane or the second organopolysiloxane) × 100 Formula (X) The viscosity at 10 rpm at 25 ° C. measured using an E-type viscometer is 1000 mPa · s or more and 100000 mPa · s or less, and
The ratio of the viscosity at 1 rpm at 25 ° C. measured using an E-type viscometer to the viscosity at 10 rpm at 25 ° C. measured using an E-type viscometer is 1.5 or more and 5.0 or less, The lens material for optical semiconductor devices according to claim 1.   The lens material for optical semiconductor devices according to claim 1, wherein the silicon oxide particles are surface-treated with an organosilicon compound.   4. The organosilicon compound is at least one selected from the group consisting of an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon compound having a polydimethylsiloxane group. Lens material for optical semiconductor devices. The lens material for optical semiconductor devices according to claim 1, wherein the second organopolysiloxane has a structural unit represented by the following formula (51-a).

In said formula (51-a), R52 and R53 represent a hydrogen atom, an aryl group, or a C1-C8 hydrocarbon group, respectively.   The lens material for an optical semiconductor device according to claim 1, wherein the second organopolysiloxane has a vinyl group bonded to a silicon atom.   The lens material for optical semiconductor devices which is a lens material for optical semiconductor devices discharged directly on the surface of the encapsulant for optical semiconductor devices that seals the optical semiconductor element using a dispenser. Lens material for optical semiconductor devices. An optical semiconductor element;
An optical semiconductor device comprising: a lens formed of the lens material for an optical semiconductor device according to claim 1. A sealant that seals the optical semiconductor element;
The optical semiconductor device according to claim 8, wherein the lens is disposed on a surface of the sealant.   The lens material for optical semiconductor devices according to claim 7 is directly discharged onto the surface of the encapsulant provided on the surface of the encapsulant so as to seal the optical semiconductor element using a dispenser. A method of manufacturing an optical semiconductor device, wherein a lens is formed on the substrate.

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