JP2013181061A - Lens material for optical semiconductor apparatus, optical semiconductor apparatus, and method for producing optical semiconductor apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lens material for an optical semiconductor apparatus, capable of enhancing thermal shock resistance of a lens and of inhibiting stickiness of a lens surface when forming the lens in the optical semiconductor apparatus.SOLUTION: A liquid lens material used for forming a lens 5 in an optical semiconductor apparatus 1 includes: a first organopolysiloxane represented by formula (1A) and having a methyl group bonded to an alkenyl group and silicon atom; a second organopolysiloxane represented by formula (51A) and having a hydrogen atom and a methyl group, both bonded to the silicon atom; a catalyst for hydrosilylation reaction; and silicon oxide particles. The containing ratios of the methyl group bonded to the silicon atom in the first and second organopolysiloxanes are 80 mol% or more.

Description

  The present invention relates to a liquid lens material for an optical semiconductor device used for forming a lens in an optical semiconductor device. The present invention also relates to an optical semiconductor device using the lens material for an optical semiconductor device and a method for 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. The lens may be disposed on the optical semiconductor element or so as to cover the optical semiconductor element.

  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

  When a conventional lens material for an optical semiconductor device as described in Patent Document 1 is used to form a lens in an optical semiconductor device, the optical semiconductor device is used in a harsh environment that is repeatedly subjected to heating and cooling. Then, the lens may be peeled off from other members. In order to reflect light reaching the back side of the light emitting element, a silver plated electrode may be formed on the back side of the light emitting element. When the lens is peeled off from other members, there is a high possibility that the silver-plated electrode comes into contact with the atmosphere. Further, there is a high possibility that the silver plating will be discolored by a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. When the color of the electrode changes, the reflectance decreases, which causes a problem that the brightness of the light emitted from the light emitting element decreases.

  Furthermore, the surface of a lens formed of a conventional lens material for an optical semiconductor device may become sticky.

  An object of the present invention is to provide a lens material for an optical semiconductor device capable of improving the thermal shock resistance of the lens and suppressing stickiness of the surface of the lens when the lens is formed in the optical semiconductor device, and the lens for the optical semiconductor device. To provide an optical semiconductor device using the material and a method of manufacturing the optical semiconductor device.

  A limited object of the present invention is to provide a lens material for an optical semiconductor device capable of forming a lens having a favorable lens shape and capable of forming a highly transparent lens, an optical semiconductor device using the lens material for an optical semiconductor device, It is to provide a method for manufacturing an optical semiconductor device.

  A more limited object of the present invention is that light that can be ejected using a dispenser or vacuum printed, and that can form a lens having a good lens shape even if ejected by a dispenser or vacuum printed. An object is to provide a lens material for a semiconductor device, an optical semiconductor device using the lens material for an optical semiconductor device, 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, which is represented by the following formula (1A) and has an alkenyl group and a methyl group bonded to a silicon atom. A first organopolysiloxane having the following formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom; a hydrosilylation reaction catalyst; In addition, the content ratio of the methyl group bonded to the silicon atom obtained from the following formula (X) in the first organopolysiloxane and the second organopolysiloxane is 80 mol% or more. A lens material for an optical semiconductor device is provided.

  In the formula (1A), a, b, and c are a / (a + b + c) = 0 to 0.30, b / (a + b + c) = 0.70 to 1.0, and c / (a + b + c) = 0 to 0. 10, R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .

  In the above formula (51A), p, q and r are p / (p + q + r) = 0.10 to 0.50, q / (p + q + r) = 0 to 0.40, r / (p + q + r) = 0.40 0.90 is satisfied, R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.

  Content ratio (mol%) of methyl groups bonded to silicon atoms = {(Average number of methyl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × Molecular weight of methyl group) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × the first organopolysiloxane or the first organopolysiloxane) 2) The average molecular weight of functional groups bonded to silicon atoms contained in one molecule of the 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.

  In another specific aspect of the lens material for an optical semiconductor device according to the present invention, in the lens material, the content ratio of hydrogen atoms bonded to silicon atoms determined by the following formula (Y) of the organopolysiloxane in the lens material The ratio (content ratio of hydrogen atoms bonded to silicon atoms / content ratio of alkenyl groups bonded to silicon atoms) to the content ratio of alkenyl groups bonded to silicon atoms obtained from the following formula (Z) of the organopolysiloxane in 0.5 or more and 5.0 or less.

  Content ratio of hydrogen atoms bonded to silicon atoms (mol%) = {(average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the first organopolysiloxane × molecular weight of hydrogen atoms) / (above Average number of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane) X blending amount of the first organopolysiloxane in the lens material / (blending amount of the first organopolysiloxane in the lens material + blending amount of the second organopolysiloxane in the lens material)} x 100+ {(Average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the second organopolysiloxane × molecular weight of hydrogen atoms) / (second Average number of functional groups bonded to silicon atoms contained per molecule of organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane) × the above 2 in the lens material of the organopolysiloxane / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material)} × 100 Formula (Y)

  Content ratio of alkenyl group bonded to silicon atom (mol%) = {(average number of alkenyl groups bonded to silicon atom per molecule of the first organopolysiloxane × the number of alkenyl groups bonded to silicon atom) Molecular weight) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × functional group bonded to silicon atoms contained in one molecule of the first organopolysiloxane) Of the first organopolysiloxane in the lens material / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material) Amount)} × 100 + {(average number of alkenyl groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane) × Molecular weight of alkenyl group bonded to silicon atom) / (average number of functional groups bonded to silicon atom contained in one molecule of the second organopolysiloxane × per molecule of the second organopolysiloxane) Average molecular weight of functional groups bonded to silicon atoms contained) × Amount of the second organopolysiloxane in the lens material / (Amount of the first organopolysiloxane in the lens material + the second Compounding amount of the organopolysiloxane in the lens material))} × 100 (Z)

  The number average molecular weight of the first organopolysiloxane represented by the above formula (1A) is preferably 20,000 or more and 100,000 or less.

  In another specific aspect of the lens material for an optical semiconductor device according to the present invention, the second organopolysiloxane represented by the above formula (51A) has an alkenyl group.

  In another specific aspect of the lens material for an optical semiconductor device according to the present invention, the second organopolysiloxane represented by the above formula (51A) has a structural unit represented by the following formula (51-a). .

  In said formula (51-a), R52 and R53 show a methyl group or a C2-C8 hydrocarbon group, respectively.

  According to a wide aspect of the present invention, there is provided an optical semiconductor device including an optical semiconductor element and a lens formed of the above-described lens material for an optical semiconductor device.

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

  According to a wide aspect of the present invention, there is provided a method for manufacturing an optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is formed using the lens material for an optical semiconductor device described above. Provided.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, in the method for manufacturing an optical semiconductor device comprising a substrate, the optical semiconductor element disposed on the substrate, and the lens, the optical semiconductor The lens material for an optical semiconductor device is directly discharged onto the substrate on which the element is arranged by using a dispenser, and the lens is formed from the lens material for an optical semiconductor device.

  In another specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, in the method for manufacturing an optical semiconductor device comprising a substrate, the optical semiconductor element disposed on the substrate, and the lens, the light The lens is formed of the lens material for an optical semiconductor device on the substrate on which the semiconductor element is arranged by using a vacuum printing apparatus.

  In another specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, a method for manufacturing an optical semiconductor device comprising the optical semiconductor element, a sealing agent that seals the optical semiconductor element, and the lens. The lens material for an optical semiconductor device is directly discharged onto the encapsulant sealing the optical semiconductor element by using a dispenser to form the lens with the lens material for an optical semiconductor device. .

  In another specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, a method for manufacturing an optical semiconductor device comprising the optical semiconductor element, a sealing agent that seals the optical semiconductor element, and the lens. Then, the lens is formed of the lens material for an optical semiconductor device by using a vacuum printing device on the sealant sealing the optical semiconductor element.

  A lens material for an optical semiconductor device according to the present invention includes a first organopolysiloxane represented by the formula (1A) and having an alkenyl group and a methyl group bonded to a silicon atom, and a silicon atom represented by the formula (51A). A second organopolysiloxane having a hydrogen atom bonded to and a methyl group bonded to a silicon atom, a hydrosilylation catalyst, and silicon oxide particles, wherein the silicon atoms in the first and second organopolysiloxanes are Since the content ratio of the bonded methyl groups is 80 mol% or more, when the lens is formed in the optical semiconductor device, the thermal shock resistance of the lens can be improved. Furthermore, stickiness of the lens surface can be suppressed.

FIG. 1 is a front sectional view showing an optical semiconductor device according to the first embodiment of the present invention. FIG. 2 is a front sectional view showing an optical semiconductor device according to the second embodiment of the present invention. 3A and 3B are front sectional views 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 used for forming a lens in an optical semiconductor device. The lens material for optical semiconductor devices according to the present invention is liquid at 25 ° C.

  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 has an alkenyl group and a methyl group bonded to a silicon atom. The second organopolysiloxane has a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom.

  The first organopolysiloxane is a first organopolysiloxane represented by the formula (1A). The second organopolysiloxane is a second organopolysiloxane represented by the formula (51A).

  Furthermore, in the lens material for optical semiconductor devices according to the present invention, the content ratios of methyl groups bonded to silicon atoms obtained from the following formula (X) in the first organopolysiloxane and the second organopolysiloxane are respectively 80 mol% or more.

  Content ratio (mol%) of methyl groups bonded to silicon atoms = {(Average number of methyl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × Molecular weight of methyl group) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × the first organopolysiloxane or the first organopolysiloxane) 2) The average molecular weight of functional groups bonded to silicon atoms contained in one molecule of the organopolysiloxane)} × 100 (Formula (X))

  The “functional group” means a group directly bonded to a silicon atom in the first organopolysiloxane or the second organopolysiloxane. In the case where there are a plurality of types of functional groups, the “molecular weight of the functional group” means the sum of “average number of functional groups × functional group molecular weight” of each functional group.

  By adopting the above composition in the lens material for an optical semiconductor device according to the present invention, the thermal shock resistance of the lens can be enhanced when the lens is formed in the optical semiconductor device. For example, the thermal cycle characteristics of the lens can be enhanced, and the gas barrier property can be enhanced. For this reason, it becomes difficult to produce a crack in a lens and it can suppress peeling of a lens. Furthermore, the stickiness of the lens surface can be suppressed by employing the above composition.

  In addition, conventional lens materials for optical semiconductor devices 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 for optical semiconductor devices, the transparency of the obtained lens may be lowered. For this reason, in an optical semiconductor device including a lens, the brightness of light emitted from the optical semiconductor element may be lowered.

  In contrast, when the lens is formed using the lens material for an optical semiconductor device according to the present invention in the optical semiconductor device by adopting the above composition in the lens material for an optical semiconductor device according to the present invention, the lens shape Can be improved. 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. Further, the use of silicon oxide particles greatly contributes to improving the vacuum printability of the lens material and the lens shape. Furthermore, by adopting the above composition in the lens material for optical semiconductor devices according to the present invention, the transparency of the lens using the lens material for optical semiconductor devices is also increased.

  Furthermore, by employing the above composition in the lens material for an optical semiconductor device according to the present invention, the heat resistance of the lens can be enhanced particularly by a combination of the specific first and second organopolysiloxanes. By increasing the heat resistance of the lens, it is possible to suppress the discoloration of the lens when exposed to high temperatures, and the lens is difficult to yellow.

  From the viewpoint of effectively increasing the heat resistance and cooling cycle characteristics of the lens, the content ratio of hydrogen atoms bonded to silicon atoms obtained from the following formula (Y) of the organopolysiloxane in the lens material is determined in the lens material. The ratio (content ratio of hydrogen atoms bonded to silicon atoms / content ratio of alkenyl groups bonded to silicon atoms) to the content ratio of alkenyl groups bonded to silicon atoms obtained from the following formula (Z) of the organopolysiloxane is: It is preferable that it is 0.5 or more and 5.0 or less. In the case where the first organopolysiloxane has a hydrogen atom bonded to a silicon atom, the content ratio of the hydrogen atom bonded to the silicon atom in the above ratio is bonded to the silicon atom of the first organopolysiloxane. The content ratio of hydrogen atoms is also considered. When the second organopolysiloxane has an alkenyl group bonded to a silicon atom, the content ratio of the alkenyl group bonded to the silicon atom in the above ratio is bonded to the silicon atom of the second organopolysiloxane. The content ratio of the alkenyl group is also considered.

  Content ratio of hydrogen atoms bonded to silicon atoms (mol%) = {(average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the first organopolysiloxane × molecular weight of hydrogen atoms) / (above Average number of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane) X blending amount of the first organopolysiloxane in the lens material / (blending amount of the first organopolysiloxane in the lens material + blending amount of the second organopolysiloxane in the lens material)} x 100+ {(Average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the second organopolysiloxane × molecular weight of hydrogen atoms) / (second Average number of functional groups bonded to silicon atoms contained per molecule of organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane) × the above 2 in the lens material of the organopolysiloxane / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material)} × 100 Formula (Y)

  The content ratio of the alkenyl group bonded to the silicon atom is obtained from the following formula (Z).

  Content ratio of alkenyl group bonded to silicon atom (mol%) = {(average number of alkenyl groups bonded to silicon atom per molecule of the first organopolysiloxane × the number of alkenyl groups bonded to silicon atom) Molecular weight) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × functional group bonded to silicon atoms contained in one molecule of the first organopolysiloxane) Of the first organopolysiloxane in the lens material / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material) Amount)} × 100 + {(average number of alkenyl groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane) × Molecular weight of alkenyl group bonded to silicon atom) / (average number of functional groups bonded to silicon atom contained in one molecule of the second organopolysiloxane × per molecule of the second organopolysiloxane) Average molecular weight of functional groups bonded to silicon atoms contained) × Amount of the second organopolysiloxane in the lens material / (Amount of the first organopolysiloxane in the lens material + the second Compounding amount of the organopolysiloxane in the lens material))} × 100 (Z)

  When the first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom, the content ratio of the hydrogen atom bonded to the silicon atom of the organopolysiloxane in the lens material is the second It represents the content ratio of hydrogen atoms bonded to silicon atoms of the organopolysiloxane, and is determined from the following formula (Y1).

  Content ratio of hydrogen atoms bonded to silicon atoms (mol%) = {(average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the second organopolysiloxane × molecular weight of hydrogen atoms) / (above Average number of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane) X blending amount of the second organopolysiloxane / (blending amount of the second organopolysiloxane in the lens material + mixing amount of the second organopolysiloxane in the lens material)} × 100・ Formula (Y1)

  In the case where the second organopolysiloxane does not have an alkenyl group bonded to a silicon atom, the content ratio of the alkenyl group bonded to the silicon atom of the organopolysiloxane in the lens material is as described above. The content ratio of the alkenyl group bonded to the silicon atom of the organopolysiloxane is represented by the following formula (Z1).

  Content ratio of alkenyl group bonded to silicon atom (mol%) = {(average number of alkenyl groups bonded to silicon atom per molecule of the first organopolysiloxane × the number of alkenyl groups bonded to silicon atom) Molecular weight) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × functional group bonded to silicon atoms contained in one molecule of the first organopolysiloxane) Of the first organopolysiloxane in the lens material / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material) Amount)} × 100 Formula (Z1)

  From the viewpoint of further increasing the heat resistance of the lens material, the above ratio (content ratio of hydrogen atoms bonded to silicon atoms / content ratio of alkenyl groups bonded to silicon atoms) is preferably 1.0 or more.

  From the viewpoint of improving the reliability of the optical semiconductor device using the lens material, the above ratio (content ratio of hydrogen atoms bonded to silicon atoms / content ratio of alkenyl groups bonded to silicon atoms) is 0.5 or more, 2 0.0 or less is preferable. When the ratio is 2.0 or less, the hardness hardly increases even when the lens material is stored at a high temperature for a long period of time. Suppression of hardness increase at high temperature leads to reduction of thermal stress generated during the cooling / heating cycle, and thus contributes to increasing the reliability of the optical semiconductor device using the lens material.

  Details of each component contained in the lens material for an optical semiconductor device according to the present invention will be described below.

(First organopolysiloxane)
The first organopolysiloxane contained in the lens material for an optical semiconductor device according to the present invention is represented by the following formula (1A) and has an alkenyl group and a methyl group bonded to a silicon atom. The first organopolysiloxane may have a hydrogen atom bonded to a silicon atom or may not have a hydrogen atom bonded to a silicon atom. The alkenyl group is preferably directly bonded to the silicon atom. The carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is in the silicon atom. It may be bonded. The methyl group is directly bonded to the silicon atom. As for said 1st organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

  In the formula (1A), a, b, and c are a / (a + b + c) = 0 to 0.30, b / (a + b + c) = 0.70 to 1.0, and c / (a + b + c) = 0 to 0. 10, R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .

In the above formula (1A), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

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

The oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ) and (R6SiO _3/2 ) in the above formula (1A) is an oxygen atom part forming a siloxane bond, an oxygen atom part of an alkoxy group, Or the oxygen atom part of a hydroxy group is shown.

  In general, in each structural unit of the above formula (1A), 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 (1A) 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 the formula (51A) described later has an alkoxy group or a hydroxy group.

  In the above formula (1A), 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 properties, the alkenyl group in the above formula (1A) is preferably a vinyl group or an allyl group, and more preferably a vinyl group.

  It does not specifically limit as a C2-C8 hydrocarbon group in said formula (1A), For example, 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 and aryl group.

From the viewpoint of enhancing the curability of the lens material and further suppressing cracking and peeling during thermal cycling, the structural unit represented by (R1R2R3SiO _1/2 ) in the above formula (1A) is such that R1 is a vinyl group. It is preferable that R2 and R3 include a structural unit representing a methyl group or a hydrocarbon group having 2 to 8 carbon atoms. That is, from the viewpoint of enhancing the curability of the lens material and further suppressing cracking and peeling during thermal cycling, the first organopolysiloxane represented by the above formula (1A) is (CH ₂ = CHR2R3SiO _{1 /} It is preferable to have a structural unit represented by ₂ ), and it is preferable to have 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). Due to the presence of the structural unit represented by the following formula (1-a), a vinyl group can be present at the terminal, and the presence of the vinyl group at the terminal increases the chance of reaction, thereby further increasing the curability of the lens material. It can be further enhanced. In the structural unit represented by the following formula (1-a), the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an 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), R2 and R3 respectively show a methyl group or a C2-C8 hydrocarbon group.

  The content ratio of the methyl group couple | bonded with the silicon atom calculated | required from the following formula (X1) in the said 1st organopolysiloxane is 80 mol% or more. When the methyl group content is 80 mol% or more, the heat resistance of the lens is considerably increased, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the luminous intensity is high. It is difficult to decrease and lens discoloration hardly occurs. The content ratio of the methyl group bonded to the silicon atom obtained from the following formula (X1) in the first organopolysiloxane is preferably 85 mol% or more, more preferably 90 mol% or more, preferably 99.9 mol%. Hereinafter, it is more preferably 99 mol% or less, and still more preferably 98 mol% or less. When the content ratio of the methyl group is not less than the preferable lower limit, the heat resistance of the lens is further increased. When the content ratio of the methyl group is not more than the above upper limit, alkenyl groups can be sufficiently introduced, and the curability of the lens material can be easily improved.

  Content ratio (mol%) of methyl groups bonded to silicon atoms = {(average number of methyl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × molecular weight of methyl groups) / (above Average number of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane) } × 100 Formula (X1)

In the first organopolysiloxane represented by the above formula (1A), 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 structural unit represented by the following formula (1-b), the oxygen atom in the Si—O—Si bond forms a siloxane bond with the adjacent silicon atom, and the adjacent structural unit and oxygen atom Sharing. Accordingly, one oxygen atom in the Si—O—Si bond is defined as “O _1/2 ”.

  In the above formulas (1-2) and (1-2b), 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 formula (1-b), formula (1-2), and formula (1-2b) are the same groups as R4 and R5 in the above formula (1A).

In the first organopolysiloxane represented by the above formula (1A), 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 formula The structure represented by (1-4), that is, the structure in which two oxygen atoms bonded to the silicon atom in the trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or the silicon atom in the trifunctional structural unit One of the oxygen atoms bonded to may include 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 formula ( The part enclosed with the broken line of the structural unit represented by 1-4-4-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 formula (1-3), formula (1-3-c), formula (1-4) and formula (1-4-c), X represents OH or OR, and OR is linear or A branched alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formula (1-c), formula (1-3), formula (1-3-c), formula (1-4) and formula (1-4-c) is the same as in formula (1A). R6 is the same group as R6.

  Formula (1-b) and Formula (1-c), Formulas (1-2) to (1-4), Formula (1-2-b), Formula (1-3-c), and Formula In (1-4-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, and an iso group. Examples thereof include a propoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group.

In the above formula (1A), the lower limit of a / (a + b + c) is 0, and the upper limit is 0.30. 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 (1A), a / (a + b + c) becomes like this. Preferably it is 0.25 or less, More preferably, it is 0.20 or less. When a is 0 and a / (a + b + c) is 0, there is no structural unit (R1R2R3SiO _1/2 ) in the above formula (1A).

  In the above formula (1A), the lower limit of b / (a + b + c) is 0.70, and the upper limit is 1.0. In the above formula (1A), b / (a + b + c) is preferably 0.75 or more, more preferably 0.80 or more. 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.

In the above formula (1A), the lower limit of c / (a + b + c) is 0, and the upper limit is 0.10. 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 the above formula (1A), c / (a + b + c) is preferably 0.05 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 (1A).

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

  In the above formula (1Aa), a and b satisfy a / (a + b) = 0 to 0.30 and b / (a + b) = 0.70 to 1.0, and at least one of R1 to R5 is alkenyl Represents at least one group, and R1 to R5 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms.

  In the above formula (1Aa), a / (a + b) is preferably 0.25 or less, more preferably 0.20 or less, and still more preferably 0.15 or less. In the above formula (1Aa), b / (a + b) is preferably 0.80 or more, more preferably 0.85 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, A peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) in the formula (1A) and the above formula (1Aa) appears in the vicinity of +10 to −5 ppm, and in the above formula (1A) and the above formula (1Aa) Each peak corresponding to the structural unit represented by (R4R5SiO _2/2 ) and the bifunctional structural unit of the above formula (1-2) appears in the vicinity of −10 to −50 ppm, and (R6SiO ₃ in the above formula (1A) _{/ 2} ) and the peaks corresponding to the trifunctional structural units of the above formula (1-3) and the above formula (1-4) appear in the vicinity of −50 to −80 ppm.

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

However, in the case where the structural unit in the above formula (1A) and the above formula (1Aa) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ By using the measurement result of H-NMR as necessary, the ratio of each structural unit in the above formula (1A) and the above formula (1Aa) can be distinguished.

(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 (51A), and includes a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom. Have. The hydrogen atom and the methyl group are directly bonded to the silicon atom. As for said 2nd organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

  In the above formula (51A), p, q and r are p / (p + q + r) = 0.10 to 0.50, q / (p + q + r) = 0 to 0.40, r / (p + q + r) = 0.40 0.90 is satisfied, R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.

In the formula (51A), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, You may have.

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

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

  It does not specifically limit as a C2-C8 hydrocarbon group in the said Formula (51A), For example, 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, allyl group and aryl 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 (51A) is such that R51 represents a hydrogen atom. It is preferable that R52 and R53 include a structural unit representing a methyl group or a hydrocarbon group having 2 to 8 carbon atoms. That is, the second organopolysiloxane has a structural unit represented by (HR52R53SiO _1/2 ) from the viewpoint of enhancing the curability of the lens material and further suppressing cracking and peeling during thermal cycling. It is preferable that it has 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). Due to the presence of the structural unit represented by the following formula (51-a), a hydrogen atom can be present at the terminal. The presence of a hydrogen atom at the end increases the opportunity for reaction and can further enhance the curability of the lens material. In the structural unit represented by the following formula (51-a), the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O _1/2 ”.

  In said formula (51-a), R52 and R53 show a methyl group or a C2-C8 hydrocarbon group, respectively.

  From the viewpoint of further enhancing the curability of the lens material and further suppressing cracking and peeling during thermal cycling, the first organopolysiloxane has a structural unit represented by the above formula (1-a). And it is particularly preferable that the second organopolysiloxane has a structural unit represented by the formula (51-a).

  From the viewpoint of further enhancing the curability of the lens material, the second organopolysiloxane represented by the above formula (51A) preferably has an alkenyl group bonded to a silicon atom. In this case, at least one of R51 to R56 represents a hydrogen atom, at least one represents a methyl group, at least one represents an alkenyl group, and R51 to R56 other than a hydrogen atom, a methyl group, and an alkenyl group. Represents a hydrocarbon group having 2 to 8 carbon atoms.

  The content ratio of the methyl group couple | bonded with the silicon atom calculated | required from the following formula (X51) in the said 2nd organopolysiloxane is 80 mol% or more. When the methyl group content is 80 mol% or more, the heat resistance of the lens is considerably increased, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the luminous intensity is high. It is difficult to decrease and lens discoloration hardly occurs. The content ratio of the methyl group bonded to the silicon atom obtained from the following formula (X51) in the second organopolysiloxane is preferably 85 mol% or more, preferably 99.9 mol% or less, more preferably 99 mol%. Hereinafter, it is more preferably 98 mol% or less. When the content ratio of the methyl group is not less than the preferable lower limit, the heat resistance of the lens is further increased. When the content ratio of the methyl group is not more than the above upper limit, hydrogen atoms bonded to silicon atoms can be sufficiently introduced, and the curability of the lens material can be easily improved.

  Content ratio (mol%) of methyl groups bonded to silicon atoms = {(average number of methyl groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane × molecular weight of methyl groups) / (above Average number of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane) } × 100 Formula (X51)

In the second organopolysiloxane represented by the above formula (51A), 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 formula (51-b), formula (51-2) and formula (51-2-b) are the same groups as R54 and R55 in the above formula (51A).

In the second organopolysiloxane represented by the above formula (51A), 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 formula (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 oxygen atoms bonded to may include 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 formula ( The part enclosed by the broken line of the structural unit represented by 51-4-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 formula (51-3), formula (51-3-c), formula (51-4) and formula (51-4-c), X represents OH or OR, and OR is linear or A branched alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formula (51-c), formula (51-3), formula (51-3-c), formula (51-4) and formula (51-4-c) is the same as in formula (51A). R56 is the same group as R56.

  Formula (51-b) and Formula (51-c), Formulas (51-2) to (51-4), Formula (51-2-b), Formula (51-3-c), Formula In (51-4-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, and an iso group. Examples thereof include a propoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group.

  In the above formula (51A), the lower limit of p / (p + q + r) is 0.10, and the upper limit is 0.50. 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 stickiness of the lens surface can be suppressed. In said formula (51A), p / (p + q + r) becomes like this. Preferably it is 0.40 or less, More preferably, it is 0.35 or less.

In the above formula (51A), the lower limit of q / (p + q + r) is 0, and the upper limit is 0.40. When q / (p + q + r) is less than or equal to the above upper limit, lens peeling can be further suppressed and stickiness of the lens surface can be suppressed. In said formula (51A), q / (p + q + r) becomes like this. Preferably it is 0.10 or more, Preferably it is 0.35 or less. In addition, when q is 0 and q / (p + q + r) is 0, the structural unit of (R54R55SiO _2/2 ) does not exist in the above formula (51A).

  In the above formula (51A), the lower limit of r / (p + q + r) is 0.40, and the upper limit is 0.90. When r / (p + q + r) is not less than the above lower limit, it is possible to further suppress the peeling of the lens and to suppress the stickiness of the lens surface. In the above formula (51A), r / (p + q + r) is preferably 0.80 or less, more preferably 0.70 or less.

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 the formula (51A) appears in the vicinity of +10 to −5 ppm, and the structural unit represented by (R54R55SiO _2/2 ) in the above formula (51A) And each peak corresponding to the bifunctional structural unit of the above formula (51-2) appears in the vicinity of −10 to −50 ppm, the structural unit represented by (R56SiO _3/2 ) in the above formula (51A), and the above Each peak corresponding to the trifunctional structural unit of formula (51-3) and formula (51-4) appears in the vicinity of −50 to −80 ppm.

Therefore, the ratio of each structural unit in the above formula (51A) 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 (51A) 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 (51A).

  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 content of the first and second organopolysiloxanes is within this range, a lens material that is more excellent in curability can be obtained. From the viewpoint of obtaining a lens material that is further excellent in curability, the content of the second organopolysiloxane is more preferably 15 parts by weight or more with respect to 100 parts by weight of the first organopolysiloxane. Preferably it is 20 weight part or more, More preferably, it is 300 weight part or less, More preferably, it is 200 weight part or less.

(Other properties of the first and second organopolysiloxanes and synthesis methods thereof)
The content of alkoxy groups in the first and second organopolysiloxanes is preferably 0.1 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. 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 silanol group can be reduced by heating under vacuum. The content of silanol groups can be measured using infrared spectroscopy.

  From the viewpoint of favorably adjusting the viscosity of the lens material within the range, the number average molecular weight of the first organopolysiloxane represented by the above formula (1A) is preferably 10,000 or more, more preferably 20,000 or more, preferably 100,000. It is as follows. From the viewpoint of adjusting the viscosity of the lens material within a favorable range, the number average molecular weight of the second organopolysiloxane represented by the above formula (51A) is preferably 1000 or more, more preferably 2000 or more, preferably 10,000. It is as follows.

  From the viewpoint of further suppressing cracking and peeling in the cooling and heating cycle, the number average molecular weight of the first organopolysiloxane represented by the above formula (1A) is preferably 20000 or more, and a higher value is considered to be preferable. It is done. However, from the viewpoint of further suppressing cracking and peeling in the cold cycle, the alkenyl group in the above formula (1A) is preferably located at the end of the organopolysiloxane, so that the higher the number average molecular weight, the higher the number average molecular weight. The content ratio of alkenyl groups and hydrogen atoms may decrease. From the viewpoint of reducing the stickiness of the lens surface, the content ratio of the alkenyl group in the above formula (1A) is preferably 0.05 mol% or more, more preferably 0.3 mol% or more.

  From the viewpoint of suppressing the stickiness of the lens surface, the number average molecular weight of the first organopolysiloxane represented by the above formula (1A) is preferably 50000 or less. In particular, when the content ratio of the alkenyl group in the formula (1A) is not less than the above lower limit, the number average molecular weight of the first organopolysiloxane represented by the formula (1A) is not more than 50,000. The stickiness of the surface can be effectively suppressed.

  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. Especially, the method of hydrolyzing and condensing an alkoxysilane compound from a viewpoint of reaction control is preferable.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method in which an alkoxysilane compound is reacted 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 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 a hydrogen atom bonded to a silicon atom into the second organopolysiloxane include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3, Examples include 3-tetramethyldisiloxane.

  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 organosilicon compound for introducing an aryl group into the first and second organopolysiloxanes as necessary include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) ) Dimethoxysilane, phenyltrimethoxysilane and the like.

  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. Among these, a potassium catalyst or a cesium 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 in the first organopolysiloxane and a hydrogen bonded to a silicon atom in the second organopolysiloxane. It is a catalyst that causes a hydrosilylation reaction with atoms.

  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 preferable because the transparency of the lens can be 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.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. 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.

  From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a harsh environment under high temperature or high humidity, and further suppressing the discoloration of the lens, the hydrosilylation reaction catalyst is An alkenyl complex of platinum is preferable. From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a harsh environment under high temperature or high humidity, and further suppressing discoloration of the lens, the platinum alkenyl complex is: It is preferably a platinum alkenyl complex obtained by reacting chloroplatinic acid hexahydrate with 6 equivalents or more of a bifunctional or higher alkenyl compound. In this case, the platinum alkenyl complex is a reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of a bifunctional or higher alkenyl compound. In addition, the use of the platinum alkenyl complex can increase the transparency of the lens. As for the said platinum alkenyl complex, only 1 type may be used and 2 or more types may be used together.

It is preferable to use the chloroplatinic acid hexahydrate (H ₂ PtCl ₆ .6H ₂ O) as a platinum raw material for obtaining the platinum alkenyl complex.

  Examples of the bifunctional or higher alkenyl compound of 6 equivalents or more for obtaining the platinum alkenyl include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl- Examples include 1,3-diphenyl-1,3-divinyldisiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

  Regarding the “equivalent” in the bifunctional or higher alkenyl compound of 6 equivalents or more, the equivalent weight of 1 mol of the bifunctional or higher alkenyl compound is 1 equivalent to 1 mol of the chloroplatinic acid hexahydrate. . It is preferable that the bifunctional or higher alkenyl compound having 6 equivalents or more is 50 equivalents or less.

  Examples of the solvent used to obtain the platinum alkenyl complex include alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol. Aromatic solvents such as toluene and xylene may be used. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  In order to obtain the platinum alkenyl complex, a monofunctional vinyl compound may be used in addition to the above components. Examples of the monofunctional vinyl compound include trimethoxyvinylsilane, triethoxyvinylsilane, and vinylmethyldimethoxysilane.

  Regarding the reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of bifunctional or higher alkenyl compound, platinum element and 6 equivalents or more of bifunctional or higher alkenyl compound are covalently bonded or distributed. Or are covalently bonded and coordinated.

  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 weight units of metal atoms (in the case of platinum alkenyl complexes, platinum atoms). When the content of the hydrosilylation reaction catalyst is 0.01 ppm or more, it is easy to sufficiently cure the lens material. When the content of the catalyst for hydrosilylation reaction is 1000 ppm or less, the problem of coloring the cured product hardly occurs. The content of the hydrosilylation catalyst is more preferably 1 ppm or more, and more preferably 500 ppm or less.

(Silicon oxide particles)
The lens material for an optical semiconductor device according to the present invention contains silicon oxide particles. By using the silicon oxide particles, the viscosity of the lens material can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the lens. Therefore, the handleability of the lens material can be improved. 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 the decrease in the viscosity due to the temperature increase of the lens material can be further suppressed.

  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 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 of the silicon oxide particles is 30 m ² / g or more, the viscosity of the lens material at 25 ° C. can be controlled within a suitable range, and a decrease in viscosity due to a temperature rise can be suppressed. When the BET specific surface area of the silicon oxide particles is 400 m ² / g or less, the aggregation of the silicon oxide particles hardly occurs, the dispersibility can be increased, and the transparency of the lens can be 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 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.

  As an example of a surface treatment method using an organosilicon compound, when an organosilicon compound having a dimethylsilyl group or an organosilicon compound having a trimethylsilyl group is used, for example, dichlorodimethylsilane, dimethyldimethoxysilane, hexamethyldisilazane, trimethylsilyl A method of surface-treating silicon oxide particles using 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 0.1 parts by weight or more, more preferably 0.5 parts by weight with respect to a total of 100 parts by weight 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, and still more preferably 20 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 contain a phosphor. Moreover, the lens material for optical semiconductor devices according to the present invention may not contain a phosphor. In this case, the lens material can be used with a phosphor added at the time of use.

  The phosphor acts to absorb light emitted from a light emitting element that is sealed using a lens material for an optical semiconductor device and generate fluorescence to finally obtain light of a desired color. . 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 content can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. The content of the phosphor 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. The content of the phosphor is preferably 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the lens material for an optical semiconductor device.

(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, and the like as necessary. An additive may be further contained.

  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. In this case, the silicon oxide particles and the phosphor may be added to the A liquid or the B liquid, respectively. In addition, by separately making the first organopolysiloxane and the hydrosilylation reaction catalyst and the second organopolysiloxane into two liquids, a first liquid and a second liquid, The storage stability of the lens material can be improved.

(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 the optical semiconductor device can be further improved, and the lens material can be accurately discharged by the dispenser. Can be increased. From the viewpoint of further improving the lens shape, further increasing the discharge accuracy of the lens material by the dispenser, and further increasing the print accuracy of the lens material in vacuum printing, the viscosity η10 is more preferably 5000 mPa · s or more, more Preferably it is 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 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 the optical semiconductor device can be further improved, and the lens material can be accurately discharged by the dispenser. Can be increased. The ratio (η1 / η10) is more preferably 1 from the viewpoint of further improving the lens shape, further increasing the discharge accuracy of the lens material by the dispenser, and further increasing the print accuracy of the lens material in vacuum printing. .8 or more, more preferably 4.0 or less.

  From the viewpoint of further improving the lens shape, further improving the discharge accuracy of the lens material by the dispenser, and further increasing the printing accuracy of the lens material in vacuum printing, the viscosity η10 is not less than the above lower limit and not more than the above upper limit. The ratio (η1 / η10) is preferably not less than the above 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. When the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.

  The curing method is not particularly limited, but it is preferable to use a step cure method. 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 material can be suppressed.

  The method for producing a lens material for an optical semiconductor device according to the present invention is not particularly limited. Alternatively, a method of mixing the first organopolysiloxane, the second organopolysiloxane, the hydrosilylation reaction catalyst, the silicon oxide particles, and other components blended as necessary under heating, etc. Can be mentioned.

  The lens material for an optical semiconductor device according to the present invention is preferably a lens material used for forming a lens using a dispenser or a vacuum printing apparatus.

  The lens material for optical semiconductor devices according to the present invention is used for forming a lens on the substrate on which the optical semiconductor element is disposed or on the sealant sealing the optical semiconductor element. A lens material is preferred.

  The lens material for an optical semiconductor device according to the present invention uses a dispenser or a vacuum printing apparatus on the substrate on which the optical semiconductor element is disposed or on the sealant that seals the optical semiconductor element. It is preferably a lens material used to form a lens.

  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. This optical semiconductor device can be obtained by forming the lens using the above-described lens material for an optical semiconductor device. The lens is obtained by curing the lens material for an optical semiconductor device according to the present invention, and is a cured product of the lens material.

  The optical semiconductor device according to the present invention preferably includes a substrate. The optical semiconductor element is preferably disposed on a substrate. In the optical semiconductor device according to the present invention, the lens is preferably disposed on the substrate on which the optical semiconductor element is disposed. The lens is preferably disposed on the surface of the optical semiconductor element, and is preferably disposed on the substrate and the optical semiconductor element.

  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, it is preferable that the lens is disposed on the sealing agent that seals 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 directly discharged onto the substrate on which the optical semiconductor element is disposed by using a dispenser, and the lens material for the optical semiconductor device is used. Preferably, the lens is formed, or the lens is formed of the lens material for an optical semiconductor device by using a vacuum printing device on the substrate on which the optical semiconductor element is disposed. It is preferable that the lens material for the optical semiconductor device is directly ejected onto the substrate on which the optical semiconductor element is disposed by using a dispenser to form the lens with the lens material for the optical semiconductor device. It is also preferable that the lens is formed of the lens material for an optical semiconductor device on the substrate on which the optical semiconductor element is disposed by using a vacuum printing apparatus.

  When obtaining the optical semiconductor device, the lens material for the optical semiconductor device is directly discharged onto the encapsulant sealing the optical semiconductor element by using a dispenser, and the optical semiconductor device is used. The lens may be formed of a lens material, or the lens may be formed of the lens material for an optical semiconductor device using a vacuum printing device on the sealant sealing the optical semiconductor element. preferable. Using the dispenser, the lens material for an optical semiconductor device is directly ejected onto the encapsulant sealing the optical semiconductor element to form the lens with the lens material for an optical semiconductor device. preferable. It is preferable that the lens is formed of the lens material for an optical semiconductor device using a vacuum printing device on the sealant sealing the optical semiconductor element.

  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.

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

  An optical semiconductor device 1 shown in FIG. 1 has a housing 2. An optical semiconductor element 3 is disposed 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 of the housing 2 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 sealing agent 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 the second embodiment of the present invention.

  In the optical semiconductor device 11 shown in FIG. 2, the optical semiconductor element 13 is disposed on the substrate 12 having the 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. Furthermore, in the optical semiconductor device 11, a lens 15 is disposed on the substrate 12 on which the optical semiconductor element 13 is disposed. The lens 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 is 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 trace 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 organopolysiloxane represented by formula (1A) To a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 476 g of dimethyldimethoxysilane and 1,3-divinyl- 5.3 g of 1,1,3,3-tetramethyldisiloxane was 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 (A).

The number average molecular weight of the obtained polymer (A) was 5830. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(Me ₂ SiO _2/2 ) _0.98 (ViMe ₂ SiO _1/2 ) _0.022 Formula (A1)
In the above formula (A1), Me represents a methyl group, and Vi represents a vinyl group. The polymer (A) had a methyl group content of 98 mol% and a vinyl group content of 1.2 mol%.

  In addition, the molecular weight of each polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 12 was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. In GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: Polystyrene) was used.

(Synthesis Example 2) Synthesis of the first organopolysiloxane represented by the formula (1A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 486 g of dimethyldimethoxysilane and 1,3-divinyl- 2.7 g of 1,1,3,3-tetramethyldisiloxane was 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 (B).

The number average molecular weight of the obtained polymer (B) was 37400. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(Me ₂ SiO _2/2 ) _0.992 (ViMe ₂ SiO _1/2 ) _0.008 Formula (B1)
In the above formula (B1), Me represents a methyl group, and Vi represents a vinyl group. The resulting polymer (B) had a methyl group content of 99 mol% and a vinyl group content of 0.5 mol%.

(Synthesis Example 3) Synthesis of first organopolysiloxane represented by formula (1A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 465 g of dimethyldimethoxysilane, 10 g of methylphenyldimethoxysilane, and 2.7 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was 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 (C).

The number average molecular weight of the obtained polymer (C) was 34,000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(Me ₂ SiO _2/2 ) _0.96 (MePhSiO _2/2 ) _0.03 (ViMe ₂ SiO _1/2 ) _0.008 ... Formula (C1)
In the above formula (C1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The resulting polymer (C) had a methyl group content of 94 mol% and a vinyl group content of 0.5 mol%.

(Synthesis Example 4) Synthesis of first organopolysiloxane represented by formula (1A) Into a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 488 g of dimethyldimethoxysilane and 1,3-divinyl- 1.2 g of 1,1,3,3-tetramethyldisiloxane was 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 (D).

The number average molecular weight of the obtained polymer (D) was 82800. 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 ) _0.998 (ViMe ₂ SiO _1/2 ) _0.002 Formula (D1)
In the above formula (D1), Me represents a methyl group, and Vi represents a vinyl group. The resulting polymer (D) had a methyl group content of 99 mol% and a vinyl group content of 0.1 mol%.

Synthesis Example 5 Synthesis of Second Organopolysiloxane Represented by Formula (51A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane and 217 g of methyltrimethoxysilane , 50 g of methyldiethoxysilane and 50 g of trimethylmethoxysilane 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, 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 (E) was obtained.

The number average molecular weight of the obtained polymer (E) was 3420. 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 ) _0.25 (MeSiO _3/2 ) _0.49 (HMeSiO _2/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.16 ... Formula (E1)
In the above formula (E1), Me represents a methyl group. In the obtained polymer (E), the content ratio of methyl groups was 91 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 6.9 mol%.

(Synthesis Example 6) Synthesis of second organopolysiloxane represented by formula (51A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane and 200 g of methyltrimethoxysilane Then, 17 g of phenyltrimethoxysilane, 50 g of methyldiethoxysilane, and 50 g of trimethylmethoxysilane 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, 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 (F) was obtained.

The number average molecular weight of the obtained polymer (F) was 3100. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(Me ₂ SiO _2/2 ) _0.25 (MeSiO _3/2 ) _0.44 (PhSiO _3/2 ) _0.05 (HMeSiO _2/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.16 ... Formula (F1)
In the above formula (F1), Me represents a methyl group and Ph represents a phenyl group. In the obtained polymer (F), the content ratio of methyl groups was 89 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 7.0 mol%.

(Synthesis Example 7) Synthesis of second organopolysiloxane represented by formula (51A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane and 200 g of methyltrimethoxysilane Then, 31 g of vinyltrimethoxysilane, 50 g of methyldiethoxysilane, and 50 g of trimethylmethoxysilane 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, 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 (G) was obtained.

The number average molecular weight of the obtained polymer (G) was 3510. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (G) had the following average composition formula (G1).

(Me ₂ SiO _2/2 ) _0.25 (MeSiO _3/2 ) _0.42 (ViSiO _3/2 ) _0.07 (HMeSiO _2/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.16 ... Formula (G1)
In the above formula (G1), Me represents a methyl group, and Vi represents a vinyl group. In the obtained polymer (G), the content ratio of methyl groups was 90 mol%, the content ratio of vinyl groups was 2.5 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 7.0 mol%.

Synthesis Example 8 Synthesis of Second Organopolysiloxane Represented by Formula (51A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane and 217 g of methyltrimethoxysilane Then, 31 g of vinyltrimethoxysilane, 40 g of 1,1,3,3-tetramethyldisiloxane and 16 g of trimethylmethoxysilane 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, 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, and reduced in pressure to remove volatile components, thereby obtaining a polymer (H).

The number average molecular weight of the obtained polymer (H) was 3200. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (H) had the following average composition formula (H1).

(Me ₂ SiO _2/2 ) _0.25 (MeSiO _3/2 ) _0.52 (ViSiO _3/2 ) _0.07 (HMe ₂ SiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _{0. 06} ... Formula (H1)
In the above formula (H1), Me represents a methyl group, and Vi represents a vinyl group. In the obtained polymer (H), the content ratio of methyl groups was 90 mol%, the content ratio of vinyl groups was 2.5 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 7.0 mol%.

(Synthesis Example 9) Synthesis of second organopolysiloxane represented by formula (51A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane and 200 g of methyltrimethoxysilane Then, 31 g of vinyltrimethoxysilane, 17 g of phenyltrimethoxysilane, 40 g of 1,1,3,3-tetramethyldisiloxane and 16 g of trimethylmethoxysilane 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, 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 (I) was obtained.

The number average molecular weight of the obtained polymer (I) was 2900. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (I) had the following average composition formula (I1).

(Me ₂ SiO _2/2 ) _0.25 (MeSiO _3/2 ) _0.47 (ViSiO _3/2 ) _0.07 (PhSiO _3/2 ) _0.05 (HMe ₂ SiO _1/2 ) _0.10 ( Me ₃ SiO _1/2 ) _0.06 ... Formula (I1)
In the above formula (I1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a vinyl group. In the obtained polymer (I), the content ratio of methyl groups was 88 mol%, the content ratio of vinyl groups was 2.5 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 7.0 mol%.

Synthesis Example 10 Synthesis of Second Organopolysiloxane Represented by Formula (51A) In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 1,1,3,3-tetramethyldisiloxane 54 g, vinyltrimethoxysilane 37 g, methyltrimethoxysilane 343 g, and trimethylmethoxysilane 84 g 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, 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 (J) was obtained.

The number average molecular weight of the obtained polymer (J) was 2320. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (J) had the following average composition formula (J1).

(HMe ₂ SiO _1/2 ) _0.09 (Me ₃ SiO _1/2 ) _0.21 (ViSiO _3/2 ) _0.07 (MeSiO _3/2 ) _0.63 Formula (J1)
In the above formula (J1), Me represents a methyl group, and Vi represents a vinyl group. In the obtained polymer (J), the content ratio of methyl groups was 93 mol%, the content ratio of vinyl groups was 2.5 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 7.0 mol%.

(Synthesis Example 11) Synthesis of an organopolysiloxane similar to the first organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 150.2 g of dimethyldimethoxysilane, 49 g of methyltrimethoxysilane, , 3-Divinyl-1,1,3,3-tetramethyldisiloxane 1.2 g and trimethylmethoxysilane 51 g 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, 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 (K) was obtained.

The number average molecular weight of the obtained polymer (K) was 8,100. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (K) had the following average composition formula (K1).

(Me ₂ SiO _2/2 ) _0.60 (MeSiO _3/2 ) _0.19 (ViMe ₂ SiO _1/2 ) _0.008 (Me ₃ SiO _1/2 ) _0.20 ... Formula (K1)
In the above formula (K1), Me represents a methyl group, and Vi represents a vinyl group. The resulting polymer (K) had a methyl group content of 94 mol% and a vinyl group content of 1.2 mol%.

Synthesis Example 12 Synthesis of Organopolysiloxane Similar to Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 180.2 g of dimethyldimethoxysilane, 51 g of methyltrimethoxysilane, vinyl 31 g of trimethoxysilane, 32 g of 1,1,3,3-tetramethyldisiloxane and 27 g of trimethylmethoxysilane 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, 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 (L) was obtained.

The number average molecular weight of the obtained polymer (L) was 3320. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (L) had the following average composition formula (L1).

(Me ₂ SiO _2/2 ) _0.6 (MeSiO _3/2 ) _0.13 (ViSiO _3/2 ) _0.07 (HMe ₂ SiO _1/2 ) _0.08 (Me ₃ SiO _1/2 ) _{0. 12} ... Formula (L1)
In the above formula (L1), Me represents a methyl group, and Vi represents a vinyl group. In the obtained polymer (L), the content ratio of methyl groups was 92 mol%, the content ratio of vinyl groups was 2.5 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 4.5 mol%.

(Catalyst for hydrosilylation reaction)
1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum

(Silicon oxide particles)
Untreated silica (“CAB-O-SIL” manufactured by Cabot, specific surface area 200 m ² / g)
Surface-treated silica 1 (“Aerosil 200” manufactured by Nippon Aerosil Co., Ltd., silicon oxide particles surface-treated with a silicon compound, specific surface area 200 m ² / g)
Surface-treated silica 2 (“R974” manufactured by Nippon Aerosil Co., Ltd., silicon oxide particles surface-treated with an organosilicon compound having a dimethylsiloxane group, specific surface area 170 m ² / g)
Surface-treated silica 3 (“R8200” manufactured by Nippon Aerosil Co., Ltd., silicon oxide particles surface-treated with an organosilicon compound having a trimethylsilyl group, specific surface area 140 m ² / g)
Surface-treated silica 4 (“RY200” manufactured by Nippon Aerosil Co., Ltd., silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g)

Example 1
Polymer A (10 g), Polymer E (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 untreated silica (“CAB-O-SIL” manufactured by Cabot, specific surface area 200 m ^{2 /} g) (0.4 g) were mixed to obtain a lens material for an optical semiconductor device.

(Examples 2 to 17 and Comparative Examples 1 and 2)
A lens material for an optical semiconductor device was obtained in the same manner as in Example 1 except that the types and blending amounts of the blending components were changed as shown in Tables 1 and 2 below.

(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). Further, a viscosity ratio (η1 / η10), which is a ratio of the viscosity η1 to the viscosity η10, was obtained.

(Lens shape (dispenser))
Polymer A (10 g), Polymer E (10 g), and platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the whole sealant) To obtain 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, the obtained lens material for an optical semiconductor device is directly discharged from a dispenser device (“SHOTMASTER-300” manufactured by Musashi Engineering Co., Ltd.) onto the flat surface (upper surface) of the sealant, and then the lens material is heated at 50 ° C. It was cured by heating for 2 hours. In this way, a lens was formed on the surface of the encapsulant so as to have a lens diameter of 5 mm and a lens height of 2.1 mm, thereby producing an optical semiconductor device.

  The shape of the lens was confirmed visually. The lens shape (dispenser) was determined based on the following criteria from the variation in lens diameter and lens height when dispensed 100 times.

[Criteria for lens shape (dispenser)]
◯: No variation in lens diameter and lens height ○: Variation in lens diameter is less than 0.1 mm, variation in lens height is less than 0.1 mm △: Variation in lens diameter is 0.1 mm or more and less than 0.2 mm, Lens height variation is 0.1 mm or more and less than 0.2 mm ×: Lens diameter variation is 0.2 mm or more, Lens height variation is 0.2 mm or more

(Lens shape (vacuum printing))
Polymer A (10 g), Polymer E (10 g), and platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the whole sealant) To obtain 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, the obtained lens material for an optical semiconductor device was obtained by using a printing plate in which a hole having a diameter of 5 mm and a thickness of 2.5 mm was formed on a flat surface (upper surface) of an encapsulant. After direct vacuum printing to a thickness of 2.1 mm, the lens material was cured by heating at 50 ° C. for 2 hours. In this way, a lens was formed on the surface of the sealant, and an optical semiconductor device was manufactured.

  The shape of the lens was confirmed visually. The lens shape (vacuum printing) was determined from the following criteria from the variation in lens diameter and lens height when 100 times of vacuum printing was performed.

[Criteria for lens shape (vacuum printing)]
◯: No variation in lens diameter and lens height ○: Variation in lens diameter is less than 0.1 mm, variation in lens height is less than 0.1 mm △: Variation in lens diameter is 0.1 mm or more and less than 0.2 mm, Lens height variation is 0.1 mm or more and less than 0.2 mm ×: Lens diameter variation is 0.2 mm or more, Lens height variation is 0.2 mm or more

(Initial transmittance)
The obtained lens material for an optical semiconductor device was heated at 150 ° C. for 2 hours to be cured to a thickness of 1 mm. The transmittance of the cured lens material for an optical semiconductor device was measured with a UV-VIS photometer (“U-3000” manufactured by Hitachi, Ltd.). The value of 400 nm was set as the initial transmittance value. The initial transmittance was determined according to the following criteria.

[Initial transmittance criteria]
◯: Initial transmittance is 90% or more ○: Initial transmittance is 85% or more and less than 90% △: Initial transmittance is 80% or more and less than 85% ×: Initial transmittance is less than 80%

(Retainability of transmittance after heat test)
The obtained lens material for an optical semiconductor device was cured by heating at 150 ° C. for 2 hours. The transmittance of the cured lens material for an optical semiconductor device was measured with a UV-VIS photometer (“U-3000” manufactured by Hitachi, Ltd.), and a value of 400 nm was defined as the initial transmittance value. As a heat resistance test, the cured lens material for an optical semiconductor device was placed in an oven at 200 ° C. for 500 hours, and the transmittance was measured with a UV-VIS photometer (“U-3000” manufactured by Hitachi, Ltd.). The transmittance retention relative to the initial value was calculated as a percentage. The transmittance retention after the heat test was determined according to the following criteria.

[Criteria for permeability retention after heat test]
◯: The transmittance retention after the heat test is 98% or more ○: The transmittance retention after the heat test is 95% or more and less than 98% △: The transmittance retention after the heat test is 90% or more , Less than 95% ×: less than 90% transmittance retention after heat test

(Decrease in adhesive strength after thermal shock test)
An optical semiconductor device prepared by evaluating the lens shape (dispenser) was prepared. The optical semiconductor device immediately after fabrication was held at −50 ° C. for 5 minutes using a liquid tank thermal shock tester (“TSB-51” manufactured by ESPEC), then heated to 135 ° C. and 5 ° C. at 135 ° C. A cold cycle test was conducted in which the temperature was lowered to -50 ° C after being held for 1 minute, and the cycle was one cycle. Twenty samples were removed after 1000 cycles.

  The adhesive strength before and after the thermal shock test was measured. The decrease in adhesive strength after the thermal shock test was determined according to the following criteria.

[Judgment criteria for decrease in adhesive strength after thermal shock test]
○: Adhesive force decrease is less than 2% ○: Adhesive force decrease is 2% or more and less than 5% Δ: Adhesion force decrease is 5% or more and less than 10% ×: Adhesion force decrease is 10% or more

(Evaluation of adhesion (stickiness) of the lens surface)
The obtained optical semiconductor device was allowed to stand for 24 hours in an atmosphere of 23 ° C. and 50 RH%. Immediately after leaving for 24 hours, the adhesiveness (stickiness) of the surface of the cured product of the lens material for optical semiconductor devices was confirmed by bringing a finger into contact with the cured product. Tackiness (stickiness) was determined according to the following criteria.

[Criteria for tackiness (stickiness)]
○○: No stickiness (stickiness) ○: Stickiness (stickiness) hardly felt △: Stickiness (stickiness) felt a little ×: Stickiness (stickiness) felt a lot

  The results are shown in Tables 1 and 2 below. Tables 1 and 2 below also show the values of the above ratios (content ratio of hydrogen atoms bonded to silicon atoms / content ratio of alkenyl groups bonded to silicon atoms).

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 (15)

A liquid lens material used to form a lens in an optical semiconductor device,
A first organopolysiloxane represented by the following formula (1A) and having an alkenyl group and a methyl group bonded to a silicon atom;
A second organopolysiloxane represented by the following formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom;
A catalyst for hydrosilylation reaction;
Including silicon oxide particles,
A lens material for an optical semiconductor device, wherein the content ratios of methyl groups bonded to silicon atoms obtained from the following formula (X) in the first organopolysiloxane and the second organopolysiloxane are each 80 mol% or more. .

In the formula (1A), a, b and c are a / (a + b + c) = 0 to 0.30, b / (a + b + c) = 0.70 to 1.0 and c / (a + b + c) = 0 to 0. 10, R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .

In the formula (51A), p, q and r are p / (p + q + r) = 0.10 to 0.50, q / (p + q + r) = 0 to 0.40, r / (p + q + r) = 0.40. 0.90 is satisfied, R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.
Content ratio (mol%) of methyl groups bonded to silicon atoms = {(Average number of methyl groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × Molecular weight of methyl group) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × the first organopolysiloxane or the first organopolysiloxane) 2) The average molecular weight of functional groups bonded to silicon atoms contained in one molecule of the 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. Bonded to the silicon atom obtained from the following formula (Z) of the organopolysiloxane in the lens material in the content ratio of the hydrogen atom bonded to the silicon atom obtained from the following formula (Y) of the organopolysiloxane in the lens material. 5. The lens material for an optical semiconductor device according to claim 1, wherein a ratio with respect to the content ratio of the alkenyl group is 0.5 or more and 5.0 or less.
Content ratio of hydrogen atoms bonded to silicon atoms (mol%) = {(average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the first organopolysiloxane × molecular weight of hydrogen atoms) / (above Average number of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the first organopolysiloxane) X blending amount of the first organopolysiloxane in the lens material / (blending amount of the first organopolysiloxane in the lens material + blending amount of the second organopolysiloxane in the lens material)} x 100+ {(Average number of hydrogen atoms bonded to silicon atoms contained in one molecule of the second organopolysiloxane × molecular weight of hydrogen atoms) / (second Average number of functional groups bonded to silicon atoms contained per molecule of organopolysiloxane × average molecular weight of functional groups bonded to silicon atoms contained per molecule of the second organopolysiloxane) × the above 2 in the lens material of the organopolysiloxane / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material)} × 100 Formula (Y)
Content ratio of alkenyl group bonded to silicon atom (mol%) = {(average number of alkenyl groups bonded to silicon atom per molecule of the first organopolysiloxane × the number of alkenyl groups bonded to silicon atom) Molecular weight) / (average number of functional groups bonded to silicon atoms contained in one molecule of the first organopolysiloxane × functional group bonded to silicon atoms contained in one molecule of the first organopolysiloxane) Of the first organopolysiloxane in the lens material / (the amount of the first organopolysiloxane in the lens material + the amount of the second organopolysiloxane in the lens material) Amount)} × 100 + {(average number of alkenyl groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane) × Molecular weight of alkenyl group bonded to silicon atom) / (average number of functional groups bonded to silicon atom contained in one molecule of the second organopolysiloxane × per molecule of the second organopolysiloxane) Average molecular weight of functional groups bonded to silicon atoms contained) × Amount of the second organopolysiloxane in the lens material / (Amount of the first organopolysiloxane in the lens material + the second Compounding amount of the organopolysiloxane in the lens material))} × 100 Formula (Z)   6. The lens material for an optical semiconductor device according to claim 1, wherein the number-average molecular weight of the first organopolysiloxane represented by the formula (1A) is 20000 or more and 100000 or less.   The lens material for optical semiconductor devices according to claim 1, wherein the second organopolysiloxane represented by the formula (51A) has an alkenyl group. 7. The optical semiconductor device according to claim 1, wherein the second organopolysiloxane represented by the formula (51A) has a structural unit represented by the following formula (51-a). Lens material.

In the formula (51-a), R52 and R53 each represent a methyl group or a hydrocarbon group having 2 to 8 carbon atoms. 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 9, wherein the lens is disposed on the sealant. An optical semiconductor device manufacturing method comprising an optical semiconductor element and a lens,
The manufacturing method of an optical semiconductor device which forms the said lens with the lens material for optical semiconductor devices of any one of Claims 1-8. A method of manufacturing an optical semiconductor device comprising a substrate, the optical semiconductor element disposed on the substrate, and the lens,
The lens is formed of the lens material for an optical semiconductor device by directly discharging the lens material for the optical semiconductor device onto the substrate on which the optical semiconductor element is disposed using a dispenser. The manufacturing method of the optical semiconductor device of description. A method of manufacturing an optical semiconductor device comprising a substrate, the optical semiconductor element disposed on the substrate, and the lens,
The method of manufacturing an optical semiconductor device according to claim 11, wherein the lens is formed from the lens material for the optical semiconductor device on a substrate on which the optical semiconductor element is disposed by using a vacuum printing apparatus. A method of manufacturing an optical semiconductor device comprising: the optical semiconductor element; a sealing agent that seals the optical semiconductor element; and the lens.
The lens is formed by the lens material for an optical semiconductor device by directly discharging the lens material for the optical semiconductor device onto the sealant sealing the optical semiconductor element by using a dispenser. Item 12. A method for manufacturing an optical semiconductor device according to Item 11. A method of manufacturing an optical semiconductor device comprising: the optical semiconductor element; a sealing agent that seals the optical semiconductor element; and the lens.
The method of manufacturing an optical semiconductor device according to claim 11, wherein the lens is formed of the lens material for the optical semiconductor device using a vacuum printing device on the sealant sealing the optical semiconductor element. .

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