JP2013191687A - Method of manufacturing optical semiconductor device, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an optical semiconductor device capable of suppressing peeling of a sealing agent or a lens from an optical semiconductor device component formed of a resin material.SOLUTION: The present invention relates to a method of manufacturing an optical semiconductor device 1 equipped with: an optical semiconductor element 3; an optical semiconductor device component which is made from a resin material, and is a package 2 or a substrate; and a sealing agent 4 or a lens arranged to contact to the optical semiconductor device component. The method of manufacturing the optical semiconductor device 1 related to the present invention includes: a step in which, before the sealing agent 4 or the lens is arranged, a surface of the optical semiconductor device component formed of the resin material that contacts the sealing agent 4 or the lens is subjected to plasma processing; and a step in which, after the plasma processing, the sealing agent 4 is arranged so as to seal the optical semiconductor element 3 while contacting to the optical semiconductor device component, otherwise, the lens is arranged over the optical semiconductor element 3 so as to contact to the optical semiconductor device component.

Description

  The present invention relates to an optical semiconductor device manufacturing method and an optical semiconductor device that include a sealant that seals an optical semiconductor element or a lens that is disposed on the optical semiconductor element.

  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 normally sealed with the sealing agent. An example of the above optical semiconductor device is disclosed in Patent Document 1 below.

For example, in a surface-mount type optical semiconductor device, an optical semiconductor element is arranged in a frame portion of a package formed of a white resin material. A sealant is filled in the frame portion of the package so as to seal the optical semiconductor element. The sealant is in contact with the package. The electrode of the optical semiconductor element is electrically connected to the lead electrode using an electrical connection member. As the electrical connection member, a bonding wire, a silver paste, or the like is used. The lead electrode connects the external power supply and the electrode of the optical semiconductor element. The lead electrode also serves as a reflector for efficiently extracting light emitted from the optical semiconductor element. For this reason, the lead electrode is generally subjected to silver plating having excellent reflectivity.

  In an optical semiconductor device, a lens may be formed using a lens material in order to control the light emission direction or to suppress the front luminance from becoming too high. An example of an optical semiconductor device in which the lens is formed is disclosed in Patent Document 2 below. Moreover, the said lens may be arrange | positioned on the surface of the said sealing agent. Further, the lens may be disposed on the surface of the substrate formed of a resin material on the optical semiconductor element. The lens is in contact with the substrate. Lead electrodes are disposed on the surface of the substrate. The electrode of the optical semiconductor element is electrically connected to the lead electrode using an electrical connection member.

JP 2011-009346 A JP 2001-196644 A

  In the conventional optical semiconductor device as described above, the package and the substrate are generally formed of a resin material. In such an optical semiconductor device, there is a problem that the sealant or the lens easily peels from the optical semiconductor device constituent member such as a package or a substrate. In particular, when the optical semiconductor device is exposed to a high temperature in a reflow process or the like, or is exposed to a thermal shock such as a thermal cycle, the sealing agent or the lens easily peels from the optical semiconductor device constituent member such as a package or a substrate. .

  Furthermore, when the sealant or the lens is peeled off from the optical semiconductor device constituent member formed of the resin material, the optical semiconductor device may cause discoloration of the electrode due to corrosive gas such as sulfur-containing gas. Further, when peeling occurs, there is a problem that the brightness of light extracted from the optical semiconductor device is lowered when the optical semiconductor device is exposed to high temperature or high humidity.

  An object of the present invention is to provide a method of manufacturing an optical semiconductor device and an optical semiconductor device capable of suppressing the sealing agent or lens from being peeled off from an optical semiconductor device constituent member formed of a resin material.

  According to a wide aspect of the present invention, an optical semiconductor element, an optical semiconductor device constituent member formed of a resin material and being a package or a substrate, and the optical semiconductor device configuration so as to seal the optical semiconductor element An optical semiconductor device manufacturing method comprising: a sealant disposed in contact with a member; or a lens disposed on the optical semiconductor element in contact with the optical semiconductor device constituent member, wherein the sealant Alternatively, before placing the lens, a step of plasma-treating the surface of the optical semiconductor device constituent member formed of a resin material in contact with the sealant or the lens, and after the plasma treatment, the optical semiconductor element is sealed. The sealing agent is disposed so as to stop and contact with the optical semiconductor device constituent member, or the sealant is placed on the optical semiconductor element so as to contact the optical semiconductor device constituent member. And a step of disposing a's, method for manufacturing the optical semiconductor device is provided.

  On the specific situation with the manufacturing method of the optical semiconductor device which concerns on this invention, the said plasma processing is atmospheric pressure plasma processing.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, the method for manufacturing an optical semiconductor device is formed of the optical semiconductor element and a resin material, has a frame portion, and is a package. An optical semiconductor device manufacturing method comprising: the optical semiconductor device constituent member; and the sealing agent disposed in the frame portion so as to be in contact with the optical semiconductor device constituent member and to seal the optical semiconductor element. A step of plasma-treating a surface of the optical semiconductor device constituting member in contact with the sealant before disposing the sealant, and sealing the optical semiconductor element after the plasma treatment; A step of arranging the sealant in the frame portion so as to be in contact with the optical semiconductor device constituent member.

  In a specific aspect of the method for producing an optical semiconductor device according to the present invention, the sealing agent and the lens are formed by curing a curable composition, and the curable composition has an alkenyl group. A first organopolysiloxane having two or more, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, and a hydrosilylation reaction catalyst.

  On the specific situation with the manufacturing method of the optical semiconductor device which concerns on this invention, the said curable composition further contains an adhesion imparting agent. The adhesion imparting agent is preferably a silane coupling agent. It is preferable that the adhesion-imparting agent contains a first silane compound having a ureido group.

  The adhesion imparting agent preferably contains a first silane compound having a ureido group and a second silane compound having an epoxy group, a vinyl group or a (meth) acryloyl group.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, among all functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of methyl groups is 80% or more, Of all the functional groups bonded to silicon atoms in the second organopolysiloxane, the number ratio of methyl groups is 80% or more.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, among all the functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of the aryl group is 30% or more and 70% or less. Of the total functional groups bonded to silicon atoms in the second organopolysiloxane, the number ratio of the aryl group is 30% or more and 70% or less.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, the first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom, and the second organopolysiloxane has an alkenyl group. Have.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, the first organopolysiloxane is represented by the following formula (1A), and has a alkenyl group and a methyl group bonded to a silicon atom. It is an organopolysiloxane, and the second organopolysiloxane is 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 a silicon atom. Or the first organopolysiloxane is represented by the following formula (1B), is a first organopolysiloxane having an aryl group and an alkenyl group, and the second organopolysiloxane is represented by the following formula: A second organopolysiloxane represented by (51B) and having a hydrogen atom bonded to an aryl group and a silicon atom.

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

  In the formula (51B), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represents at least one aryl group, at least one represents a hydrogen atom, and R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, the first organopolysiloxane represented by the formula (1A) or the formula (1B) has a hydrogen atom bonded to a silicon atom. The second organopolysiloxane represented by the formula (51A) or the formula (51B) has an alkenyl group, and in the formula (51A), at least one of R51 to R56 has a hydrogen atom. And at least one represents a methyl group, at least one represents an alkenyl group, R51 to R56 other than a hydrogen atom, a methyl group and an alkenyl group represent a hydrocarbon group having 2 to 8 carbon atoms, and the above formula ( 51B), at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, at least one represents an alkenyl group, an aryl group, a hydrogen atom and an alkenyl R51~R56 except represents a hydrocarbon group having 1 to 8 carbon atoms.

  In a specific aspect of the method for manufacturing an optical semiconductor device according to the present invention, the first organopolysiloxane is represented by the formula (1A), and the second organopolysiloxane is represented by the formula (51A). expressed.

  According to a wide aspect of the present invention, an optical semiconductor element, an optical semiconductor device constituent member formed of a resin material and being a package or a substrate, and the optical semiconductor device configuration so as to seal the optical semiconductor element The optical semiconductor device constituent member, comprising: a sealant disposed in contact with a member, or a lens disposed on the optical semiconductor element so as to contact the optical semiconductor device constituent member, and formed of a resin material A semiconductor device is provided in which a surface in contact with the sealant or the lens is subjected to plasma treatment.

  In a specific aspect of the optical semiconductor device according to the present invention, the plasma processing is atmospheric pressure plasma processing.

  In a specific aspect of the optical semiconductor device according to the present invention, the optical semiconductor device is formed of the optical semiconductor element and a resin material, has a frame portion, and is a package. And the sealing agent disposed in the frame so as to seal the optical semiconductor element and in contact with the optical semiconductor device constituent member, the optical semiconductor device configuration formed of a resin material The surface of the member in contact with the sealant is plasma treated.

  The method for producing an optical semiconductor device of the present invention includes a step of plasma-treating a surface of the optical semiconductor device constituent member formed of a resin material in contact with the sealant or the lens before disposing the sealant or the lens, After the plasma treatment, a sealing agent is disposed so as to seal the optical semiconductor element and in contact with the optical semiconductor device constituent member, or a lens is disposed on the optical semiconductor element so as to contact the optical semiconductor device constituent member. Therefore, it is possible to provide an optical semiconductor device capable of suppressing the sealant or the lens from being peeled off from the optical semiconductor device constituent member formed of the resin material.

  In the optical semiconductor device according to the present invention, the surface of the optical semiconductor device constituting member formed of the resin material that is in contact with the sealant or the lens is subjected to plasma treatment. Therefore, the sealant or the lens is formed of the resin material. Peeling from the optical semiconductor device constituent member can be suppressed.

1A and 1B are a front sectional view and a perspective view showing an optical semiconductor device obtained by the method for manufacturing 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 obtained by the method for manufacturing an optical semiconductor device according to the second embodiment of the present invention. FIG. 3 is a front sectional view showing an optical semiconductor device obtained by the method for manufacturing an optical semiconductor device according to the third embodiment of the present invention.

  Details of the present invention will be described below.

  An optical semiconductor device manufacturing method according to the present invention includes: an optical semiconductor element; an optical semiconductor device constituent member that is formed of a resin material and that is a package or a substrate; and the optical semiconductor element is sealed. It is a manufacturing method of an optical semiconductor device provided with the sealing agent arrange | positioned in contact with a semiconductor device structural member, or the lens arrange | positioned on the said optical semiconductor element so that the said optical semiconductor device structural member may be contact | connected. The method for manufacturing an optical semiconductor device according to the present invention includes the step of arranging the surface of the optical semiconductor device constituting member formed of a resin material in contact with the sealing agent or the lens before the sealing agent or the lens is disposed. A step of performing plasma treatment, and after the plasma treatment, a sealing agent is disposed so as to seal the optical semiconductor element and in contact with the constituent member of the optical semiconductor device, or the optical semiconductor device on the optical semiconductor element And a step of arranging a lens so as to be in contact with the structural member.

  By adopting the above-described configuration, particularly when the surface of the optical semiconductor device constituent member formed of the resin material is subjected to plasma treatment, the sealing agent or the lens is removed from the optical semiconductor device constituent member formed of the resin material. An optical semiconductor device capable of suppressing peeling is obtained.

  An optical semiconductor device according to the present invention includes an optical semiconductor element, an optical semiconductor device constituent member formed of a resin material and being a package or a substrate, and the optical semiconductor device configuration so as to seal the optical semiconductor element. A sealant disposed in contact with the member, or a lens disposed on the optical semiconductor element so as to be in contact with the optical semiconductor device constituent member. In the optical semiconductor device according to the present invention, the surface of the optical semiconductor device constituent member formed of a resin material that is in contact with the sealing agent or the lens is subjected to plasma treatment.

  In the optical semiconductor device, the optical semiconductor device in which the sealing agent or the lens is formed of the resin material is obtained by adopting the above-described configuration, in particular, that the optical semiconductor device constituent member formed of the resin material is subjected to plasma treatment. It can suppress peeling from a structural member. In particular, even if the optical semiconductor device is exposed to a high temperature in a reflow process or the like, or is exposed to a thermal shock such as a cooling / heating cycle, peeling of the sealant or the lens from the optical semiconductor device constituent member can be suppressed.

  Suppresses discoloration of electrodes due to corrosive gas such as sulfur-containing gas in optical semiconductor device as a result of suppressing sealing agent or lens from peeling from optical semiconductor device components formed of resin material can do. Furthermore, even if the optical semiconductor device is exposed to high temperature or high humidity, it is possible to suppress the peeling of the sealant or the lens from the optical semiconductor device constituent member, thereby reducing the brightness of light extracted from the optical semiconductor device. Can be suppressed. Therefore, in the present invention, an optical semiconductor device with excellent reliability can be obtained.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

  1A and 1B are a front sectional view and a perspective view showing an optical semiconductor device obtained by the method for manufacturing an optical semiconductor device according to the first embodiment of the present invention.

  An optical semiconductor device 1 shown in FIG. 1 includes a package 2 that is an optical semiconductor device constituent member formed of a resin material. Package 2 is also called a housing. The package 2 has a frame portion 2a. The frame part 2a is annular. The package 2 has a recess on the upper side. The frame portion 2 a is an outer wall portion that constitutes a part of the concave portion of the package 2. An optical semiconductor element 3 is disposed in the frame 2 a of the package 2. The inner surface of the frame part 2a has light reflectivity. The periphery of the optical semiconductor element 3 is surrounded by the inner surface of the frame portion 2a. The optical semiconductor element 3 is a light emitting element such as an LED.

  The inner surface of the frame portion 2a is formed so that the diameter of the inner surface becomes larger toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light that has reached the inner surface of the frame portion 2 a is reflected by the inner surface and travels forward of the optical semiconductor element 3.

  A sealing agent 4 is filled in the frame portion 2 a so as to seal the optical semiconductor element 3. The optical semiconductor element 3 is sealed with a sealant 4 in the frame 2 a of the package 2. The periphery of the sealing agent 4 is surrounded by the inner surface of the frame portion 2a. The outer peripheral surface of the sealing agent 4 is in contact with the inner peripheral surface of the frame portion 2a. Therefore, the sealing agent 4 is in contact with the package 2 formed of a resin material on the inner surface of the frame portion 2a. It is preferable that the sealing agent 4 is formed by hardening the sealing agent which is a curable composition.

  The optical semiconductor device 1 has a lead frame 5. An optical semiconductor element 3 is arranged on the lead frame 5. Further, a part of the package 2 is disposed on the lead frame 5, and the frame portion 2a is disposed. A part of the package 2 is also disposed between the plurality of lead frames 5 and below the lead frames 5. A part of the package 2 is disposed below the portion of the lead frame 5 where the optical semiconductor element 3 is disposed above. The package 2 disposed on the lead frame 5 and the package 2 disposed below the lead frame 5 are integrally formed, but may be formed of different members.

  The optical semiconductor element 3 is connected to the lead frame 5 using a die bond material 6. A bonding pad (not shown) provided on the optical semiconductor element 3 and the lead frame 5 are electrically connected by a bonding wire 7. The sealing agent 4 is filled in the frame portion 2 a so as to seal the bonding wire 7.

  FIG. 2 is a front sectional view showing an optical semiconductor device obtained by the method for manufacturing an optical semiconductor device according to the second embodiment of the present invention.

  An optical semiconductor device 11 illustrated in FIG. 2 includes a package 2 that is an optical semiconductor device constituent member formed of a resin material. An optical semiconductor element 3 is disposed in the frame 2 a of the package 2. The sealing agent 12 is filled in the frame portion 2 a so as to seal the optical semiconductor element 3. That is, the optical semiconductor element 3 is sealed with the sealant 12 in the frame 2 a of the package 2. The sealant 12 is in contact with the package 2 formed of a resin material on the inner surface of the frame portion 2a. Therefore, the sealing agent 12 is in contact with the package 2 formed of a resin material. It is preferable that the sealing agent 12 is formed by hardening the sealing agent which is a curable composition.

  Further, in the optical semiconductor device 11, a lens 13 is disposed on the sealant 12. The outer peripheral edge of the lower surface of the lens 13 is in contact with the upper surface of the frame portion 2a. Therefore, the lens 13 is in contact with the package 2 made of a resin material on the upper surface of the frame portion 2a. The lens 13 is preferably formed by curing a lens material that is a curable composition.

  FIG. 3 is a front sectional view showing an optical semiconductor device obtained by the method for manufacturing an optical semiconductor device according to the third embodiment of the present invention.

  In the optical semiconductor device 21 shown in FIG. 3, an optical semiconductor element 23 is arranged on a substrate 22 on which terminals 26 are arranged on the upper surface. The substrate 22 is an optical semiconductor device constituent member made of a resin material. An electrode 23 a disposed on the upper surface of the optical semiconductor element 23 and a terminal 26 disposed on the upper surface of the substrate 22 are electrically connected by a bonding wire 24. Further, in the optical semiconductor device 21, a lens 25 is disposed on the optical semiconductor element 23. The lens 25 covers the surface of the optical semiconductor element 23 and the bonding wire 24. The lens 25 is in contact with the substrate 22 made of a resin material. The lens 25 is preferably formed by curing a lens material that is a curable composition.

  In the optical semiconductor devices 1 and 11 shown in FIGS. 1 and 2, the surface of the package 2 in contact with the sealants 4 and 12 and the lens 13 is subjected to plasma treatment. The surface of the package 2 is plasma-treated before the sealing agents 4 and 12 and the lens 13 are arranged, that is, before the sealing agents 4 and 12 and the lens 13 are in contact with each other. Sealants 4 and 12 and a lens 13 are arranged so as to come into contact with the package 2 after the plasma treatment. Moreover, the sealing agents 4 and 12 and the lens 13 are disposed so as to be in contact with the frame portion 2a.

  In the optical semiconductor device 21 shown in FIG. 3, the surface of the substrate 22 in contact with the lens 25 is subjected to plasma treatment. The surface of the substrate 22 is subjected to plasma treatment before the lens 25 is disposed, that is, before the lens 25 contacts. A lens is disposed so as to be in contact with the substrate 22 after the plasma processing.

  The structures shown in FIGS. 1 to 3 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.

  The surface of the optical semiconductor device constituent member formed of a resin material that contacts the sealing agent is preferably subjected to plasma treatment, and the surface of the optical semiconductor device constituent member formed of a resin material that contacts the lens is plasma treated. It is also preferable to process. Moreover, it is preferable to plasma-process a frame part.

  Since the processing is easy, the plasma processing is preferably atmospheric pressure plasma processing. Moreover, it can suppress more effectively that sealing agent or a lens peels from the optical semiconductor device structural member formed of the resin material by performing atmospheric pressure plasma processing. The plasma treatment method includes a direct method in which a plasma discharge is generated between two electrodes to which a voltage is applied and a workpiece is passed between the electrodes, and an electrode in which the plasma discharge is generated. There is known a remote method in which a plasma process is performed by blowing gas from between electrodes through a gas flow between the electrodes and spraying the plasma gas on an object to be processed. Of these, the remote method is preferable. It is preferable to plasma-treat the surface of the optical semiconductor device constituent member in contact with the sealing agent or the lens by spraying plasma gas onto the optical semiconductor device constituent member formed of a resin material by a remote method.

  In the direct method, when an optical semiconductor device constituent member is introduced into plasma, arc discharge is likely to occur on a metal lead frame. For this reason, damage may occur to the lead electrode, the optical semiconductor device constituent member, and the optical semiconductor element. In contrast, the remote method can avoid damage due to discharge.

  As a method of generating plasma in the plasma treatment, there are a first method using a gas in which a small amount of helium gas is mixed as a discharge gas, and a second method of applying a voltage as a pulse wave. As a method for generating plasma, there is also a third method for generating plasma in a reduced pressure atmosphere. Plasma generated by any one of the first, second, and third methods may be used. Plasma generated by a method different from the first, second, and third methods may be used. In the third method, a chamber and a decompression pump for decompressing are required, and in addition to the processing apparatus becoming large and expensive, the inside of the chamber is decompressed after the object to be processed is placed in the chamber, After performing the plasma treatment, a complicated operation of releasing the reduced pressure and taking out the object to be processed is necessary. Therefore, the third method has a problem that it is inferior in productivity.

  In the third method, the kinetic energy of gas molecules converted into plasma by depressurization becomes very high, and the discoloration due to so-called “burning” may occur in the package resin that is the object to be processed.

  A gas such as helium, argon, nitrogen, neon, or oxygen is used as a gas for performing plasma discharge in the plasma treatment. Moreover, you may use these mixed gas and air as discharge gas. From the viewpoint of reducing cost, it is preferable to use argon or nitrogen.

  Further, when argon or a mixed gas of nitrogen and oxygen, a gas containing nitrogen and oxygen, or air is used as a discharge gas, oxygen is easily introduced into the surface of the optical semiconductor device constituent member during plasma processing, and efficiency In particular, it is possible to improve the adhesiveness.

  When the oxygen concentration in the discharge gas is high, the processing efficiency is improved. On the other hand, when the oxygen concentration becomes high, there is a high possibility that the resin on the surface of the optical semiconductor device constituting member is oxidized and deteriorated, markedly oxidized, carbonized by combustion, or ignited. For this reason, it is preferable that the oxygen concentration in discharge gas is 30 volume% or less.

  The plasma processing conditions may be appropriately set depending on the structure and capability of the plasma processing apparatus used. Changes in surface energy due to plasma treatment can be evaluated by contact angle with water. For example, the water contact angle on a clean surface of a polyphthalamide resin generally used as an optical semiconductor device constituent member is 75 to 80 degrees. After the plasma treatment, the water contact angle is preferably 60 degrees or less, more preferably 55 degrees or less, and still more preferably 45 degrees or less.

  The plasma treatment may be performed before the placement of the optical semiconductor element or after the placement of the optical semiconductor device. The plasma treatment may be performed after the connection between the electrode of the optical semiconductor element and the lead frame, or may be performed before the connection between the electrode of the optical semiconductor element and the lead frame.

  The optical semiconductor device constituent member is formed of a resin material and is a package or a substrate. The said optical semiconductor device structural member is arrange | positioned in the position which contact | connects a sealing agent or a lens. The optical semiconductor device constituent member is preferably a package, and is preferably a substrate. The optical semiconductor device constituent member and the package preferably have a frame portion. The sealant or the lens is preferably arranged in the frame part or on the frame part, and more preferably in the frame part. When the sealant or the lens is disposed in the frame portion, the sealant and the lens have a portion disposed in the frame portion and a portion disposed outside the frame portion. It may be. The optical semiconductor element is preferably arranged in the frame portion.

  The resin material that is a material of the optical semiconductor device constituent member includes a resin. The resin may be a thermoplastic resin or a thermosetting resin. Examples of the resin include polyphthalamide, polycyclohexylene terephthalate, epoxy resin, and silicone resin. Among them, polyphthalamide is widely used as the resin in the package for filling the sealant.

  The resin material may contain a filler in addition to the resin. A white filler is preferably used as the filler. Examples of the white filler include titanium oxide and zinc oxide. When the resin material contains a white filler, the light reflectivity of the surface of the optical semiconductor device constituting member is increased. As a result, the amount of light reflected when the light emitted from the optical semiconductor element reaches the surface of the optical semiconductor device constituent member in the optical semiconductor device increases. Accordingly, the brightness of the light extracted from the optical semiconductor device is increased.

  The optical semiconductor device constituting member and the package can be obtained by arranging a lead frame serving as an electrode at a predetermined position and molding the resin material by transfer molding or the like. The lead frame is embedded in, for example, the optical semiconductor device constituent member and the package.

  Examples of the lead frame include a lead frame having a copper foil surface plated with silver. The copper foil is generally processed into a predetermined shape by punching or etching.

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

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

  Specific examples of the optical semiconductor device 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. It is suitably used for displays, decorations, various lights and switching elements.

  The shape of the lens 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 shape of the lens may be a part of a sphere or a part of a spheroid. preferable.

  The sealant and the lens are preferably formed by curing a curable composition. The curable composition includes a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, and a hydrosilylation reaction catalyst. It is preferable. From the viewpoint of further suppressing the sealing agent and the lens (cured product) from peeling from the optical semiconductor device constituent member, the curable composition preferably contains an adhesion-imparting agent.

  By using the curable composition containing the first and second organopolysiloxanes, the hydrosilylation reaction catalyst, and the adhesion-imparting agent, the optical semiconductor device is used in a harsh environment under high temperature and high humidity. However, it becomes difficult for the sealant and the lens to be peeled off from the optical semiconductor device constituent member.

  For example, when the said sealing agent or the said lens is formed using the said curable composition, a sealing agent and a lens become difficult to peel from a draft conductor apparatus structural member. For example, the material of the package that contacts the sealant or the lens may be polyphthalamide (PPA). Moreover, in order to reflect the light which reached the back surface side of the light emitting element, an electrode plated with silver may be formed on the back surface of the light emitting element. It is strongly required that the cured product has high adhesion to a package or electrode formed of such PPA. When the cured product is peeled off from the package or the electrode or the adhesion is low, the amount of light (luminous intensity) emitted from the optical semiconductor device decreases.

  In an optical semiconductor device, it is difficult to sufficiently enhance the adhesion to an optical semiconductor device constituent member formed of a sealing agent and a lens resin. As a result of intensive studies, the present inventor has adopted a composition containing a first silane compound having a ureido group together with the first and second organopolysiloxanes and the hydrosilylation reaction catalyst, thereby providing a sealing agent and a lens resin. It has been found that the adhesion to an optical semiconductor device constituent member formed of a material can be sufficiently enhanced.

  The first organopolysiloxane is represented by the formula (1A) and is a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom, or represented by the formula (1B) and an aryl A first organopolysiloxane having a group and an alkenyl group is preferred. The first organopolysiloxane represented by the formula (1A) and the formula (1B) has two or more alkenyl groups. However, a first organopolysiloxane different from the first organopolysiloxane represented by the formula (1A) or the formula (1B) may be used. When the second organopolysiloxane has an alkenyl group, the first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom. The first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom.

  The second organopolysiloxane is a second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom, or the formula (51B) And is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom. The second organopolysiloxane represented by the formula (51A) and the formula (51B) has two or more hydrogen atoms bonded to silicon atoms. However, a second organopolysiloxane different from the second organopolysiloxane represented by the formula (51A) or the formula (51B) may be used.

  From the viewpoint of improving the adhesion of the cured product to the object to be bonded and further improving the heat resistance and gas barrier properties of the cured product and the pot life of the curable composition, the first organopolysiloxane is represented by the formula A first organopolysiloxane represented by (1A) having an alkenyl group and a methyl group bonded to a silicon atom, and the second organopolysiloxane is represented by the formula (51A) and bonded to a silicon atom Or a second organopolysiloxane having a methyl group bonded to a hydrogen atom and a silicon atom, or the first organopolysiloxane represented by the formula (1B) having an aryl group and an alkenyl group. 1 and the second organopolysiloxane is represented by the formula (51B) and is bonded to an aryl group and a silicon atom. It is preferred that the second organopolysiloxane having a hydrogen atom.

  In addition, when a cured product of a conventional curable composition is used in a harsh environment such as a temperature cycle that repeatedly receives heating and cooling, the cured product is cracked or the cured product is peeled off from a package or the like. Sometimes. In particular, a cured product of a conventional curable composition has a problem that heat resistance is low.

  From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the first organopolysiloxane is a first organopolysiloxane represented by the formula (1A) and having an alkenyl group and a methyl group bonded to a silicon atom. The second organopolysiloxane is preferably the second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom.

  From the viewpoint of obtaining a cured product that is more excellent in heat resistance, it is preferable that the number ratio of methyl groups in all functional groups bonded to silicon atoms in the first organopolysiloxane is 80% or more. From the viewpoint of obtaining a cured product that is more excellent in heat resistance, it is preferable that the number ratio of methyl groups is 80% or more among all functional groups bonded to silicon atoms of the second organopolysiloxane.

  Among all the functional groups bonded to silicon atoms in the first and second organopolysiloxanes, the number ratio of methyl groups is more preferably 85% or more, still more preferably 90% or more, and preferably 99.9. % Or less, more preferably 99% or less, and still more preferably 98% or less. When the number ratio of methyl groups is 80% or more, the heat resistance of the cured product is increased, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the cured product can be used. Is less likely to occur and the luminous intensity is less reduced. Moreover, the heat resistance of hardened | cured material becomes still higher that the number ratio for which the said methyl group accounts is more than the said minimum. When the number ratio of the methyl groups is not more than the above upper limit, alkenyl groups can be sufficiently introduced into the first organopolysiloxane, and hydrogen atoms bonded to silicon atoms can be sufficiently introduced into the second organopolysiloxane, It is easy to improve the curability of the curable composition.

  As described above, a silver-plated electrode may be formed on the back surface of the light emitting element in order to reflect the light reaching the back side of the light emitting element. When a crack occurs in the sealant or the lens, or the sealant peels from the constituent member of the optical semiconductor device, the silver-plated electrode is exposed to the atmosphere or easily exposed to the atmosphere. As a result, the silver plating may 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. The encapsulant or lens, which is a cured product of the curable composition, has a high gas barrier property against corrosive gas, thereby suppressing discoloration of silver plating and suppressing a decrease in brightness of light emitted from the light emitting element. it can.

  From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the first organopolysiloxane is the first organopolysiloxane represented by the formula (1B) and having an aryl group and an alkenyl group, and the first The second organopolysiloxane represented by the formula (51B) is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.

  From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, among all the functional groups bonded to the silicon atom of the first organopolysiloxane, the number ratio of the aryl group is 30% or more and 70% or less. Is preferred. From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the ratio of the number of aryl groups in the total functional groups bonded to silicon atoms of the second organopolysiloxane is 30% or more and 70% or less. Is preferred.

  Among all the functional groups bonded to silicon atoms in the first and second organopolysiloxanes B, the number ratio of the aryl group is more preferably 35% or more, and more preferably 65% or less. When the number ratio of the aryl group is equal to or more than the above lower limit, the gas barrier property of the cured product is further enhanced, and cracks and peeling are less likely to occur in the cured product. When the number ratio of the aryl group is less than or equal to the above upper limit, peeling of the cured product is more difficult to occur.

  In addition, when the aryl group is a phenyl group, the number ratio of the aryl group indicates the number ratio of the phenyl group.

  The curing temperature of the curable composition is not particularly limited. The curing temperature of the curable composition is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 160 ° C. or lower. When the curing temperature is equal to or higher than the lower limit, the curing of the curable composition proceeds sufficiently. When the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.

  Hereinafter, the detail of each component contained in the said curable composition is demonstrated.

(First organopolysiloxane)
The first organopolysiloxane contained in the curable composition has two or more alkenyl groups. 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. As for said 1st organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the first organopolysiloxane is represented by the following formula (1A), and includes a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom. Siloxane (hereinafter sometimes referred to as first organopolysiloxane A) is preferred. The first organopolysiloxane A is preferably a first organopolysiloxane which does not have a hydrogen atom bonded to a silicon atom but has an alkenyl group and a methyl group bonded to a silicon atom.

  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. .

  From the viewpoint of obtaining a cured product having further excellent gas barrier properties, the first organopolysiloxane is represented by the following formula (1B) and has a first organopolysiloxane having an aryl group and an alkenyl group (hereinafter referred to as the first organopolysiloxane). 1 may be referred to as organopolysiloxane B). The first organopolysiloxane B is preferably a first organopolysiloxane which does not have a hydrogen atom bonded to a silicon atom and has an aryl group and an alkenyl group. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group.

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

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

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

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

  In general, in each structural unit of the above formula (1A) and the above formula (1B), 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) and the above formula (1B) has an alkoxy group or a hydroxy group, an unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains slightly. Indicates that The same applies to the case where each structural unit of formula (51A) and formula (51B) described later has an alkoxy group or a hydroxy group.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing the gas barrier property, the alkenyl group in the first organopolysiloxane and the alkenyl group in the above formula (1A) and the above formula (1B) are preferably vinyl groups or allyl groups. More preferably, it is a group. From the viewpoint of further improving the curability of the curable composition, the first organopolysiloxane preferably has 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. As a C1-C8 hydrocarbon group in the said Formula (1B), the group similar to a C2-C8 hydrocarbon group in the said Formula (1A) is mentioned, Furthermore, a methyl group is mentioned.

  From the viewpoint of further improving the storage stability of the curable composition, the first organopolysiloxane A preferably has an aryl group. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group. Among all the functional groups bonded to silicon atoms in the first organopolysiloxane A, the number ratio of the aryl group is preferably 0.5% or more, preferably 10% or less, more preferably 5% or less. When the number ratio of the aryl groups in the first organopolysiloxane A is not more than the above upper limit, the heat resistance of the cured product is further improved.

In the first organopolysiloxane represented by the above formula (1A) and the above formula (1B), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula ( The structure represented by 1-2), that is, the 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 may be included.

(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) and the above formula (1B). It is.

In the first organopolysiloxane represented by the above formula (1A) and the above formula (1B), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) has the following formula ( 1-3) or a structure represented by formula (1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or trifunctional One of the oxygen atoms bonded to the silicon atom in the structural unit 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) represents the above formula (1A) and It is the same group as R6 in the above formula (1B).

  Formula (1-b) and Formula (1-c), Formulas (1-2) to (1-4), Formula (1-2-b), Formula (1-3-c) and Formula (1) In 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 isopropoxy group. , Isobutoxy group, sec-butoxy group and 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 cured product is further increased, and peeling of the cured product 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. When b / (a + b + c) is not less than the above lower limit, the cured product does not become too hard, and cracks hardly occur in the cured product. In the above formula (1A), b / (a + b + c) is preferably 0.75 or more, more preferably 0.80 or more.

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 of the curable composition, and the adhesiveness of the cured product 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). Thereby, it becomes difficult to produce a crack in hardened | cured material further, and hardened | cured material becomes much more difficult to peel from an optical semiconductor device structural member.

  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 0.75 or more, more preferably 0.80 or more, and further preferably 0.85 or more.

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

  In the above formula (1B), b / (a + b + c) is 0.40 or more and 1.0 or less. When b / (a + b + c) is not less than the above lower limit, the cured product does not become too hard, and cracks hardly occur in the cured product. In the above formula (1B), b / (a + b + c) is preferably 0.50 or more.

In the above formula (1B), c / (a + b + c) is 0 or more and 0.50 or less. When c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced. In the above formula (1B), c / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less, and still more preferably 0.35 or less. In addition, when c is 0 and c / (a + b + c) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1B).

  C / (a + b + c) in the above formula (1B) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1B) is preferably the first organopolysiloxane represented by the following formula (1Bb). As a result, cracks are less likely to occur in the cured product, and peeling of the cured product is further less likely to occur.

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

  A / (a + b) in the above formula (1Bb) is preferably 0.45 or less, more preferably 0.40 or less. In the above formula (1Bb), b / (a + b) is preferably 0.55 or more, more preferably 0.60 or more.

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

Therefore, the ratio of each structural unit in the above formula (1A) and the above formula (1B) 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 above formula (1A) and the above formula (1B) 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 results of H-NMR as necessary, the ratio of each structural unit in the above formula (1A) and the above formula (1B) can be distinguished.

(Second organopolysiloxane)
The second organopolysiloxane contained in the curable composition has two or more hydrogen atoms bonded to silicon atoms. The hydrogen atom is 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.

  From the viewpoint of obtaining a cured product that is more excellent in heat resistance, the second organopolysiloxane is represented by the following formula (51A) and has a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom. A second organopolysiloxane (hereinafter sometimes referred to as a second organopolysiloxane A) is preferred.

  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 and 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.

  From the viewpoint of obtaining a cured product that is more excellent in gas barrier properties, the second organopolysiloxane is represented by the following formula (51B), and includes a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom. Siloxane (hereinafter sometimes referred to as second organopolysiloxane B) is preferred. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group.

  In the above formula (51B), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represents at least one aryl group, at least one represents a hydrogen atom, and R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group.

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

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

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

  It does not specifically limit as a C2-C8 hydrocarbon group in said Formula (51A), The hydrocarbon group similar to C2-C8 in said Formula (1A) is mentioned. As a C1-C8 hydrocarbon group in the said Formula (51B), the group similar to a C2-C8 hydrocarbon group in the said Formula (1A) is mentioned, Furthermore, a methyl group is mentioned.

  From the viewpoint of further improving the curability of the curable composition, the second organopolysiloxane preferably has an alkenyl group, and more preferably has a vinyl group. In this case, in the above formula (51A), at least one of R51 to R56 represents a silicon atom, at least one represents a methyl group, at least one represents an alkenyl group, a hydrogen atom, a methyl group, and R51 to R56 other than the alkenyl group represent a hydrocarbon group having 2 to 8 carbon atoms. In the above formula (51B), at least one of R51 to R56 represents an aryl group, at least one represents a silicon atom, at least one represents an alkenyl group, and other than an aryl group, a hydrogen atom, and an alkenyl group R51 to R56 represent a hydrocarbon group having 2 to 8 carbon atoms.

  From the viewpoint of further improving the storage stability of the curable composition, the second organopolysiloxane A preferably has an aryl group. Examples of the aryl group include an unsubstituted phenyl group and a substituted phenyl group. Among all the functional groups bonded to silicon atoms in the second organopolysiloxane A, the number ratio of the aryl group is preferably 0.5% or more, preferably 10% or less, more preferably 5% or less. When the number ratio of aryl groups in the second organopolysiloxane A is not more than the above upper limit, the heat resistance of the cured product is further improved.

In the second organopolysiloxane represented by the above formula (51A) and the above formula (51B), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula ( The structure represented by 51-2), that is, the 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 may be included.

(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) and the above formula (51B). It is.

In the second organopolysiloxane represented by the above formula (51A) and the above formula (51B), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) has the following formula ( 51-3) or a structure represented by 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 trifunctional One of the oxygen atoms bonded to the silicon atom in the structural unit 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) represents the above formula (51A) and It is the same group as R56 in the above formula (51B).

  Formula (51-b) and Formula (51-c), Formulas (51-2) to (51-4), Formula (51-2-b), Formula (51-3-c), and Formula (51) In 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 isopropoxy group. , Isobutoxy group, sec-butoxy group and 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 hardness of the cured product is increased, adhesion of scratches and dust can be prevented, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed. . In said formula (51A), p / (p + q + r) becomes like this. Preferably it is 0.45 or less, More preferably, it is 0.40 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) exceeds 0, the cured product does not become too hard and cracks are hardly generated in the cured product. In said formula (51A), q / (p + q + r) becomes like this. Preferably it is 0.10 or more, More preferably, it is 0.15 or more. 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, the hardness of the cured product is increased, and scratches and dust can be prevented from adhering. When r / (p + q + r) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.

  In the above formula (51B), p / (p + q + r) is 0.05 or more and 0.50 or less. When p / (p + q + r) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed. In said formula (51B), p / (p + q + r) becomes like this. Preferably it is 0.10 or more, Preferably it is 0.45 or less.

  In the above formula (51B), q / (p + q + r) is 0.05 or more and 0.50 or less. When q / (p + q + r) is not less than the above lower limit, the cured product does not become too hard and cracks are hardly generated in the cured product. When q / (p + q + r) is not more than the above upper limit, the gas barrier property of the cured product is further enhanced. In said formula (51B), q / (p + q + r) becomes like this. Preferably it is 0.10 or more, More preferably, it is 0.45 or less.

  In said formula (51B), r / (p + q + r) is 0.20 or more and 0.80 or less. When r / (p + q + r) is equal to or greater than the above lower limit, the hardness of the cured product is increased, scratches and dust can be prevented, the heat resistance of the cured product is increased, and the thickness of the cured product is less likely to decrease in a high temperature environment. Become. When r / (p + q + r) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.

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

Therefore, the ratio of each structural unit in the above formula (51A) and the above formula (51B) 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 above formula (51A) and the above formula (51B) cannot be distinguished by the ²⁹ Si-NMR measurement based on the above 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 (51A) and the above formula (51B) can be distinguished.

  The content of the second organopolysiloxane is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, preferably 100 parts by weight of the first organopolysiloxane. 400 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less. When the content of the first and second organopolysiloxanes is not less than the above lower limit and not more than the above upper limit, a curable composition more excellent in curability can be obtained.

(Other properties of the first and second organopolysiloxanes and synthesis methods thereof)
The number average molecular weight (Mn) of the first organopolysiloxane is preferably 500 or more, more preferably 1000 or more, still more preferably 5000 or more, preferably 200000 or less, more preferably 100000 or less, still more preferably 60000 or less, Particularly preferred is 10,000 or less, and most preferred is 8000 or less. The number average molecular weight (Mn) of the first organopolysiloxane represented by the above formula (1A) is preferably 500 or more, more preferably 1000 or more, further preferably 5000 or more, preferably 200000 or less, more preferably 100000. Hereinafter, it is more preferably 60000 or less. The number average molecular weight (Mn) of the first organopolysiloxane represented by the above formula (1B) is preferably 500 or more, more preferably 1000 or more, preferably 10,000 or less, more preferably 8000 or less. The number average molecular weight (Mn) of the second organopolysiloxane is preferably 500 or more, more preferably 1000 or more, preferably 20000 or less, more preferably 10,000 or less. When the number average molecular weight is not less than the above lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the cured product is hardly reduced under a high temperature environment. When the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.

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

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

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the curable composition comprises hydrosilylation of an alkenyl group in the first organopolysiloxane and a hydrogen atom bonded to a silicon atom in the second organopolysiloxane. The catalyst to be reacted.

  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. Since the transparency of the cured product is increased, a platinum-based catalyst is preferable.

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

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

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

  In the curable composition, the content of the catalyst for hydrosilylation reaction is preferably 0.01 ppm or more, more preferably 1 ppm or more, preferably in terms of weight units of metal atoms (platinum atoms in the case of platinum alkenyl complexes). Is 1000 ppm or less, more preferably 500 ppm or less. When the content of the hydrosilylation reaction catalyst is not less than the above lower limit, it is easy to sufficiently cure the curable composition. When the content of the catalyst for hydrosilylation reaction is not more than the above upper limit, the problem of coloring of the cured product hardly occurs.

(Adhesive agent)
From the viewpoint of further suppressing the sealing agent and the lens (cured product) from peeling from the optical semiconductor device constituent member, the curable composition preferably contains an adhesion-imparting agent. The adhesion imparting agent is preferably a silane coupling agent. From the viewpoint of further suppressing the sealing agent and the lens from peeling from the optical semiconductor device constituent member, the curable composition and the adhesion-imparting agent preferably contain a first silane compound having a ureido group. . By using the first silane compound, even when the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the cured product obtained by curing the curable composition is less likely to be peeled off from the adhesion target.

  From the viewpoint of further suppressing the peeling of the cured product from the object to be bonded, the first silane compound is preferably a first silane compound represented by the following formula (S1).

  In the above formula (S1), X1 represents an alkoxy group, X2 and X3 each represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and R4 is a single bond directly bonding a nitrogen atom and a silicon atom. Or a hydrocarbon group having 1 to 8 carbon atoms.

  The content of the adhesion-imparting agent is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 10 parts by weight with respect to a total of 100 parts by weight of the first and second organopolysiloxanes. Part or less, more preferably 5 parts by weight or less, still more preferably 3 parts by weight or less. When the content of the adhesion-imparting agent is equal to or more than the lower limit, peeling of the cured product from the object to be bonded can be further suppressed. If the content of the adhesion-imparting agent is not more than the above upper limit, the excess first silane coupling agent is less likely to volatilize, and the thickness of the cured product is less likely to decrease in a high temperature environment.

  The content of the first silane compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight in total for the first and second organopolysiloxanes. 5 parts by weight or less, more preferably 3 parts by weight or less. When the content of the first silane compound is equal to or higher than the lower limit, peeling of the cured product from the adhesion target can be further suppressed. If the content of the first silane compound is less than or equal to the above upper limit, the excess first silane coupling agent is less likely to volatilize, and the thickness of the cured product is less likely to decrease in a high temperature environment.

  The adhesion-imparting agent preferably contains a second silane compound different from the first silane compound having a ureido group. By using the second silane compound together with the first silane compound, peeling of the cured product from the object to be bonded can be further suppressed. As for the said 2nd silane compound, only 1 type may be used and 2 or more types may be used together.

  The second silane compound is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Examples include 3- (meth) acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

  The “(meth) acryloyl” refers to acryloyl and methacryloyl. The “(meth) acryloxy” refers to acryloxy and methacryloxy.

  From the viewpoint of further suppressing the peeling of the cured product from the object to be bonded, the second silane compound preferably has an epoxy group, a vinyl group, or a (meth) acryloyl group.

  From the viewpoint of further suppressing peeling of the cured product from the object to be bonded, the second silane compound is 3-glycidoxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Vinyltrimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane is preferred.

  The content of the second silane compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight based on the total of the first and second organopolysiloxanes. 5 parts by weight or less, more preferably 3 parts by weight or less. When the content of the second silane compound is equal to or more than the lower limit, peeling of the cured product from the adhesion target can be further suppressed. If the content of the second silane compound is less than or equal to the above upper limit, the excess second silane coupling agent is less likely to volatilize, and the thickness of the cured product is less likely to decrease in a high temperature environment.

(Silicon oxide particles)
The curable composition preferably further includes silicon oxide particles. In the case where the curable composition is an encapsulant for optical semiconductor devices, the encapsulant preferably further contains silicon oxide particles. By using the silicon oxide particles, the viscosity of the curable composition can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the cured product. Therefore, the handleability of the curable composition is improved.

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

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 at 25 ° C. of the curable composition can be controlled within a suitable range, and the decrease in the 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 cured product can be further increased. it can.

  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 cured product with less volatile components and higher transparency.

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

  The content of the silicon oxide particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, still more preferably 1 with respect to 100 parts by weight of the total of the first and second organopolysiloxanes. Part by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, 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 curable composition can be controlled to a more appropriate range, and the transparency of the cured product is further enhanced.

(Phosphor)
The curable composition may further contain a phosphor. When the curable composition is a sealant, the sealant preferably further contains a phosphor. Moreover, the said curable composition does not need to contain the fluorescent substance. In this case, a phosphor may be added when using the curable composition.

  The phosphor acts, for example, to absorb light emitted from a light-emitting element that is sealed using the curable composition and generate fluorescence, thereby finally obtaining light of a desired color. To do. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color is 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 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 preferably 40 parts by weight or less with respect to 100 parts by weight of the curable composition. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the curable composition.

(Other ingredients)
The curable composition further contains an additive such as a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, a heat conductive filler, or a flame retardant as necessary. You may go out.

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

Example 1
Synthesis of the first organopolysiloxane:
In a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 486 g of dimethyldimethoxysilane and 2.7 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are placed, and at 50 ° C. Stir. 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 37400. 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 ) _0.992 (ViMe ₂ SiO _1/2 ) _0.008 Formula (A1)
In the above formula (A1), Me represents a methyl group, and Vi represents a vinyl group. The number ratio of the methyl group in the obtained polymer (A) was 99%.

  The molecular weight of the polymer was measured by GPC measurement after 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 of the second organopolysiloxane:
In a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 90.2 g of dimethyldimethoxysilane, 217 g of methyltrimethoxysilane, 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, reduced in pressure to remove volatile components, and polymer (B) was obtained.

The number average molecular weight of the obtained polymer (B) was 3420. 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 ) _0.25 (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 (B1)
In the above formula (B1), Me represents a methyl group, and Vi represents a vinyl group. The number ratio of the methyl group in the obtained polymer (B) was 90%.

Preparation of the curable composition:
Polymer A (10 g), Polymer B (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.05 g) were mixed and defoamed to obtain a curable composition (a).

Fabrication of optical semiconductor device:
A light emitting element having a main emission peak of 460 nm is mounted by a die-bonding material in the upper frame portion of a silver-plated polyphthalamide package with a lead electrode, and the light emitting element and the lead electrode are connected by a gold wire. A light emitting diode package having a structure as described above was prepared. A glass plate was affixed to the opposite side (downward) of the package frame side. In a remote type atmospheric pressure plasma processing apparatus (AMP-400-R type manufactured by AM Technology Co., Ltd.), while blowing a plasma gas obtained by atmospheric pressure plasma using nitrogen gas as a discharge gas at a speed of 0.5 m / min, The light emitting diode package was passed once (number of passes) to perform atmospheric pressure plasma treatment in the frame of the package.

  Next, the curable composition (a) is poured into the frame of the package, heated at 80 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to be cured to form a sealant. Produced.

(Example 2)
An optical semiconductor device was manufactured in the same manner as in Example 1 except that in the manufacture of the optical semiconductor device, the type of discharge gas was changed to a discharge gas in which nitrogen and oxygen were mixed at a volume ratio of 95: 5.

(Example 3)
In the production of the optical semiconductor device, an optical semiconductor device was produced in the same manner as in Example 1 except that the number of passes was changed from once to twice.

Example 4
Preparation of the curable composition:
Polymer A (10 g) synthesized in Example 1, Polymer B (10 g) synthesized in Example 1, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (curable composition) The total amount of platinum metal is 10 ppm by weight), 3-ureidopropyltriethoxysilane (0.03 g), and 3-glycidoxypropyltrimethoxysilane (0.03 g) are mixed and defoamed. To obtain a curable composition (b).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 3 except that the curable composition (a) was changed to the curable composition (b).

(Example 5)
Synthesis of the first organopolysiloxane:
In a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 474 g of dimethyldimethoxysilane, 10 g of diphenyldimethoxysilane, 1.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and 200 g of dimethylformamide 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 38000. 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 ) _0.987 (Ph ₂ SiO _2/2 ) _0.010 (ViMe ₂ SiO _1/2 ) _0.003 Formula (C1)
In the above formula (C1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The number ratio of the methyl groups in the obtained polymer (C) was 99%.

Synthesis of the second organopolysiloxane:
In a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 150 g of dimethyldimethoxysilane, 360 g of methyltrimethoxysilane, 52 g of vinyltrimethoxysilane, 67 g of 1,1,3,3-tetramethyldisiloxane, and trimethyl 21 g of methoxysilane was added and stirred at 50 ° C. Into this, a solution of 2.6 g of hydrochloric acid and 220 g of water was slowly added dropwise. After the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (D) was obtained.

The number average molecular weight of the obtained polymer (D) was 3480. 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 ) _0.20 (MeSiO _3/2 ) _0.59 (ViSiO _3/2 ) _0.07 (HMe ₂ SiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _{0. 04} ... Formula (D1)
In the above formula (D1), Me represents a methyl group, and Vi represents a vinyl group. The number ratio of the methyl groups in the obtained polymer (D) was 90%.

Preparation of the curable composition:
Polymer C (12 g), Polymer D (8 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.05 g) were mixed and defoamed to obtain a curable composition (c).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (c).

(Example 6)
Preparation of the curable composition:
Polymer C (12 g) synthesized in Example 5, Polymer D (8 g) synthesized in Example 5, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (curable composition) The total amount of platinum metal is 10 ppm by weight), 3-ureidopropyltriethoxysilane (0.03 g), and 3-glycidoxypropyltrimethoxysilane (0.03 g) are mixed and defoamed. To obtain a curable composition (d).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (d).

(Example 7)
Preparation of the curable composition:
Polymer C (12 g) synthesized in Example 5, Polymer D (8 g) synthesized in Example 5, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (curable composition) The total amount of platinum metal is 10 ppm by weight), 3-ureidopropyltriethoxysilane (0.06 g), and 3-glycidoxypropyltrimethoxysilane (0.06 g) are mixed and defoamed. To obtain a curable composition (e).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (e).

(Example 8)
Synthesis of the first organopolysiloxane:
In a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 6.3 g of trimethylmethoxysilane, 89 g of dimethyldimethoxysilane, 318 g of diphenyldimethoxysilane, and 119 g of vinylmethyldimethoxysilane were added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 107 g of water was slowly added dropwise thereto, and after the addition, the mixture was stirred at 50 ° C. for 6 hours to be reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (E).

The number average molecular weight (Mn) of the obtained polymer (E) was 5000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (E) had the following average composition formula (E1).

(Me ₃ SiO _1/2 ) _0.01 (Me ₂ SiO _2/2 ) _0.24 (Ph ₂ SiO _2/2 ) _0.45 (ViMeSiO _2/2 ) _0.30 ... Formula (E1)
In the above formula (E1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The number ratio of the phenyl groups in the obtained polymer (E) was 52 mol%.

Synthesis of the second organopolysiloxane:
In a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer, 31 g of trimethylmethoxysilane, 40 g of 1,1,3,3-tetramethyldisiloxane, 110 g of diphenyldimethoxysilane, 268 g of phenyltrimethoxysilane, and vinyltri 45 g of methoxysilane was added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 116 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 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 (Mn) of the obtained polymer (F) was 1100. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.19 (Ph ₂ SiO _2/2 ) _0.16 (PhSiO _3/2 ) _0.46 (ViSiO _3/2 ) _{0. 10} : Formula (F1)
In the above formula (F1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The number ratio of the phenyl groups in the obtained polymer (F) was 51 mol%.

Preparation of the curable composition:
Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.05 g) were mixed and defoamed to obtain a curable composition (f).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (f).

Example 9
Preparation of the curable composition:
Polymer E (10 g) synthesized in Example 8, Polymer F (10 g) synthesized in Example 8, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (curable composition) The total amount of platinum metal is 10 ppm by weight), 3-ureidopropyltriethoxysilane (0.03 g), and 3-glycidoxypropyltrimethoxysilane (0.03 g) are mixed and defoamed. To obtain a curable composition (g).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (g).

(Example 10)
Preparation of the curable composition:
Polymer A (10 g) synthesized in Example 1, Polymer B (10 g) synthesized in Example 1, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (curable composition) The amount of platinum metal was 10 ppm by weight with respect to the entire product) and defoamed to obtain a curable composition (h).

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (h).

(Example 11)
Preparation of the curable composition:
Polymer A (10 g) synthesized in Example 1, Polymer B (10 g) synthesized in Example 1, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (curable composition) The total amount of platinum metal is 10 ppm by weight) and 3-glycidoxypropyltrimethoxysilane (0.05 g) are mixed and defoamed to obtain a curable composition (i). .

Fabrication of optical semiconductor device:
An optical semiconductor device was produced in the same manner as in Example 1 except that the curable composition (a) was changed to the curable composition (i) and the number of passes was changed from 1 to 2 times. did.

(Comparative Example 1)
In the production of the optical semiconductor device, an optical semiconductor device was produced in the same manner as in Example 1 except that the atmospheric pressure plasma treatment was not performed.

(Comparative Example 2)
In the production of the optical semiconductor device, an optical semiconductor device was produced in the same manner as in Example 5 except that the atmospheric pressure plasma treatment was not performed.

(Comparative Example 3)
In the production of the optical semiconductor device, an optical semiconductor device was produced in the same manner as in Example 8 except that atmospheric pressure plasma treatment was not performed.

(Comparative Example 4)
In the production of the optical semiconductor device, an optical semiconductor device was produced in the same manner as in Example 10 except that atmospheric pressure plasma treatment was not performed.

(Evaluation)
Using the obtained optical semiconductor device, the following evaluation items were evaluated.

(Gas corrosion test)
The obtained optical semiconductor device was fixed with a double-sided tape on a slide glass with the light emitting surface facing up. Next, 0.2 g of sulfur was placed in a glass container with a lid having a capacity of 120 mL, and a slide glass on which the optical semiconductor device was fixed was placed in the glass container so that the optical semiconductor device and sulfur were not in direct contact. Thereafter, the glass container was sealed and placed in an oven at 80 ° C. After being placed in the oven, changes in the silver-plated lead electrodes were visually observed after 8 hours, 16 hours, 24 hours, 48 hours, and 72 hours. The gas corrosion test was judged according to the following criteria.

○○: No change in the silver electrode ○: About 10% of the area of the silver electrode changes to black, or the entire surface changes slightly △: About half of the area of the silver electrode changes to black, or the entire surface Changes to brown ×: almost the entire surface of the silver electrode changes to black

(Thermal shock test)
The obtained optical semiconductor device 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 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. 20 samples were taken out after 500 cycles, 1000 cycles, 1500 cycles, 2000 cycles and 3000 cycles, respectively.

  The sample was observed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation). Observe whether the sealant of 20 samples has cracks or whether the sealant is peeled off from the package or the electrode. I counted.

(Reflow test)
The obtained optical semiconductor device was conditioned for 168 hours in an atmosphere of a temperature of 30 ° C. and a humidity of 70%. Thereafter, the optical semiconductor device was passed through a reflow apparatus ("UNI-5016F" manufactured by Nippon Antom Co., Ltd.) three times under conditions of preheating 150 ° C x 120 seconds + reflow 260 ° C (max.) X 30 seconds.

  Thereafter, the sample was dipped in red ink at 23 ° C. for 4 hours, and whether or not ink permeation due to peeling was observed at the interface between the sealant (cured product) and the package was observed with a stereomicroscope (“SMZ-10” manufactured by Nikon Corporation). ). Ten samples were tested, and the number of samples (NG number) in which red ink penetration was observed was counted.

(High temperature and high humidity energization test)
About the obtained optical semiconductor device, the luminous intensity when a current of 20 mA was passed through the light emitting element was measured using a photometric measuring device (“OL770” manufactured by Optronic Laboratories) at a temperature of 23 ° C. (hereinafter, “initial” Called “luminosity”).

  Next, the optical semiconductor device was placed in a chamber at 85 ° C. and a relative humidity of 85 RH% in a state where a current of 20 mA was passed through the light emitting element, and left for 1000 hours. After 1000 hours, at a temperature of 23 ° C., the light intensity when a current of 20 mA was passed through the light emitting element was measured using a light intensity measuring device (“OL770” manufactured by Optronic Laboratories), and the rate of decrease in light intensity relative to the initial light intensity was measured. Calculated. The high temperature and high humidity energization test was judged according to the following criteria.

[Criteria for high-temperature and high-humidity current test]
○: Decrease rate of luminosity is less than 5% △: Decrease rate of luminosity is 5% or more and less than 10% ×: Decrease rate of luminosity is 10% or more

  The results are shown in Tables 1 and 2 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Package 2a ... Frame part 3 ... Optical semiconductor element 4 ... Sealing agent 5 ... Lead frame 6 ... Die bond material 7 ... Bonding wire 11 ... Optical semiconductor device 12 ... Sealing agent 13 ... Lens 21 ... Light Semiconductor device 22 ... Substrate 23 ... Optical semiconductor element 23a ... Electrode 24 ... Bonding wire 25 ... Lens 26 ... Terminal

Claims (17)

An optical semiconductor element, an optical semiconductor device constituent member made of a resin material and being a package or a substrate, and a seal disposed so as to seal the optical semiconductor element and in contact with the optical semiconductor device constituent member An optical semiconductor device manufacturing method comprising: a stopper, or a lens disposed on the optical semiconductor element so as to contact the optical semiconductor device constituent member;
Plasma-treating the surface of the optical semiconductor device constituting member formed of a resin material in contact with the sealant or the lens before placing the sealant or the lens;
After the plasma treatment, a sealing agent is disposed so as to seal the optical semiconductor element and to be in contact with the optical semiconductor device constituent member, or to be in contact with the optical semiconductor device constituent member on the optical semiconductor element. And a step of arranging a lens.   The method for manufacturing an optical semiconductor device according to claim 1, wherein the plasma treatment is an atmospheric pressure plasma treatment. The optical semiconductor element is formed of a resin material, has a frame portion, and is an optical semiconductor device constituent member that is a package; and the optical semiconductor element is sealed so as to be in contact with the optical semiconductor device constituent member An optical semiconductor device manufacturing method comprising the sealing agent disposed in the frame so as to include:
Before placing the sealant, plasma treating the surface of the optical semiconductor device constituting member in contact with the sealant; and
3. The light according to claim 1, further comprising a step of placing the sealing agent in the frame portion so as to seal the optical semiconductor element and to be in contact with the optical semiconductor device constituent member after the plasma treatment. A method for manufacturing a semiconductor device. The sealant and the lens are formed by curing a curable composition,
The curable composition includes a first organopolysiloxane having two or more alkenyl groups, a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms, and a hydrosilylation reaction catalyst. The manufacturing method of the optical semiconductor device of any one of Claims 1-3.   The method for manufacturing an optical semiconductor device according to claim 4, wherein the curable composition further contains an adhesion-imparting agent.   The method for manufacturing an optical semiconductor device according to claim 5, wherein the adhesion-imparting agent is a silane coupling agent.   The method for manufacturing an optical semiconductor device according to claim 5, wherein the adhesion-imparting agent contains a first silane compound having a ureido group.   The optical semiconductor device according to claim 7, wherein the adhesion-imparting agent includes a first silane compound having a ureido group and a second silane compound having an epoxy group, a vinyl group, or a (meth) acryloyl group. Method. Among all functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of methyl groups is 80% or more,
The manufacturing of the optical semiconductor device according to any one of claims 4 to 8, wherein a number ratio of methyl groups among all functional groups bonded to silicon atoms in the second organopolysiloxane is 80% or more. Method. Of all functional groups bonded to silicon atoms in the first organopolysiloxane, the number ratio of the aryl group is 30% or more and 70% or less,
The light according to any one of claims 4 to 8, wherein the number ratio of the aryl group among all functional groups bonded to silicon atoms in the second organopolysiloxane is 30% or more and 70% or less. A method for manufacturing a semiconductor device. The first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom;
The method for manufacturing an optical semiconductor device according to claim 4, wherein the second organopolysiloxane has an alkenyl group. The first organopolysiloxane is represented by the following formula (1A), is a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom, and the second organopolysiloxane is: The second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom, or the first organopolysiloxane is represented by the following formula (1B And a hydrogen atom bonded to an aryl group and a silicon atom, the first organopolysiloxane having an aryl group and an alkenyl group, wherein the second organopolysiloxane is represented by the following formula (51B): The manufacturing method of the optical semiconductor device of any one of Claims 4-8 which is 2nd organopolysiloxane which has these.

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

In the formula (51B), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represents at least one aryl group, at least one represents a hydrogen atom, and R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group. The first organopolysiloxane represented by the formula (1A) or the formula (1B) does not have a hydrogen atom bonded to a silicon atom,
The second organopolysiloxane represented by the formula (51A) or the formula (51B) has an alkenyl group,
In the formula (51A), 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 other than a hydrogen atom, a methyl group, and an alkenyl group. -R56 represents a C2-C8 hydrocarbon group,
In the formula (51B), at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, at least one represents an alkenyl group, and R51 other than an aryl group, a hydrogen atom, and an alkenyl group. -R56 represents the manufacturing method of the optical semiconductor device of Claim 12 showing a C1-C8 hydrocarbon group.   The optical semiconductor device according to claim 12 or 13, wherein the first organopolysiloxane is represented by the formula (1A), and the second organopolysiloxane is represented by the formula (51A). Method. An optical semiconductor element;
An optical semiconductor device constituent member formed of a resin material and being a package or a substrate;
A sealing agent disposed so as to seal the optical semiconductor element and in contact with the optical semiconductor device constituent member, or a lens disposed on the optical semiconductor element so as to contact the optical semiconductor device constituent member; With
A semiconductor device, wherein a surface of the optical semiconductor device constituting member formed of a resin material that is in contact with the sealant or the lens is subjected to plasma treatment.   The optical semiconductor device according to claim 15, wherein the plasma treatment is an atmospheric pressure plasma treatment. The optical semiconductor element;
The optical semiconductor device constituting member that is formed of a resin material, has a frame portion, and is a package;
The sealing agent disposed in the frame portion so as to seal the optical semiconductor element and in contact with the optical semiconductor device constituent member,
The optical semiconductor device according to claim 15 or 16, wherein a surface of the optical semiconductor device constituent member formed of a resin material that is in contact with the sealing agent is subjected to plasma treatment.

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