JP6672631B2 - Silicone resin tablet, substrate for mounting optical semiconductor element, method for manufacturing the same, and optical semiconductor device - Google Patents

Description

  The present invention relates to a silicone resin tablet, a substrate for mounting an optical semiconductor element, a method for manufacturing the same, and an optical semiconductor device.

  Thermosetting resins are used for a wide range of applications because they exhibit various excellent properties derived from their unique crosslinked structure. One application is an optical semiconductor device in which an optical semiconductor element such as an LED (Light Emitting Diode) is combined with a phosphor. BACKGROUND ART Optical semiconductor devices have been applied to various applications such as outdoor displays, portable liquid crystal backlights, and in-vehicle applications because of their advantages such as high energy efficiency and long life, and their demands are expanding.

  Patent Document 1 discloses a substrate for mounting an optical semiconductor element using a thermosetting resin composition containing an epoxy resin as a material of a reflector. Patent Document 1 discloses that a reflector is produced by transfer-molding a resin tablet made of the thermosetting resin composition.

  Here, when manufacturing a molded body by transfer molding of a resin tablet, continuous operation is being studied. For example, Patent Literature 2 discloses a resin encapsulation molding apparatus for encapsulating and molding an electronic component mounted on a lead frame with a resin material, and more particularly, a resin molding die having a plurality of pots and a plunger. There is disclosed a resin tablet transfer / supply device used in conjunction with a plunger-type resin sealing / molding device, and a resin tablet transfer / supply method using the transfer / supply device.

  On the other hand, the use of a silicone resin as a material for the reflector is also being studied. For example, Patent Document 3 discloses a resin composition for an optical semiconductor element housing packaging package using a silicone resin having a structure in which one of a vinyl group and an allyl group and a hydrogen atom are directly bonded to a silicon atom. Is disclosed.

JP 2006-140207 A JP-A-8-108432 JP 2009-21394 A

  Since the resin composition described in Patent Document 3 is in a paste form, it is difficult to form a resin tablet from the resin composition. In addition, when a resin tablet is formed using a resin composition containing a silicone resin as in Patent Document 3, if a transport and supply device as described in Patent Document 2 is applied, the shape of the tablet during transport of the tablet is reduced. The tablet is deformed, and it is difficult to supply the tablet to the transfer molding device by automatic conveyance.

  The present invention has been made in view of the above circumstances, the shape is difficult to deform, silicone resin tablet excellent in transportability and automatic transportability, an optical semiconductor element mounting substrate using the same and a method of manufacturing the same, and It is an object to provide an optical semiconductor device.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and found that a silicone resin tablet containing a specific silicone resin is hardly deformed and has excellent transportability and automatic transportability. It was completed.

  The present invention relates to a silicone resin tablet containing a silicone resin and a pigment, wherein the silicone resin contains a solid silicone resin at 25 ° C. and a thermosetting silicone resin liquid at 25 ° C.

  The silicone resin tablet of the present invention contains a silicone resin and a pigment, and the proportion of the aryl group or the cycloalkyl group bonded to the silicon atom is based on the total amount of the hydrocarbon group bonded to the silicon atom. Of a silicone resin of 20 mol% or more and a thermosetting silicone resin liquid at 25 ° C.

Further, the silicone resin tablet of the present invention contains a silicone resin and a pigment, and the silicone resin has the following silicon-containing bonding units Q, T, and D in a solid-state ²⁹ Si-NMR spectrum measured by a DD / MAS method. A silicone resin having a ratio of Q + T: D of 1: 0 to 1: 0.5 between a signal area derived from Q and T and a signal area derived from D, and thermosetting liquid at 25 ° C. An embodiment containing a hydrophilic silicone resin can be taken. Here, Q represents a silicon-containing bonding unit having four oxygen atoms bonded to one silicon atom, and T represents three oxygen atoms bonded to one silicon atom and a hydrogen atom or monovalent. Represents a silicon-containing bonding unit having one organic group, and D represents a silicon-containing bonding unit having two oxygen atoms bonded to one silicon atom and two hydrogen atoms or monovalent organic groups. Represent.

  Further, the silicone resin tablet of the present invention may include a silicone resin and a pigment, and may have a type A durometer hardness of 50 or more.

  In the silicone resin tablet, the pigment is selected from the group consisting of titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, antimony oxide, zirconium oxide, and inorganic hollow particles from the viewpoint of improving the light reflectance of the molded article. At least one white pigment can be included.

  The present invention relates to a cured product formed using the above-mentioned silicone resin tablet. In another aspect, the present invention relates to a substrate for mounting an optical semiconductor element, comprising a molded body formed from the silicone resin tablet. The optical semiconductor element mounting substrate may have a concave portion having a bottom surface and a wall surface, and the bottom surface of the concave portion may be an optical semiconductor element mounting portion. In this case, at least a part of the wall surface of the concave portion is a molded body formed from the silicone resin tablet. The optical semiconductor element mounting substrate is provided between the substrate, the first connection terminal and the second connection terminal provided on the substrate, and between the first connection terminal and the second connection terminal. And a molded article formed from the silicone resin tablet.

  In still another aspect, the present invention relates to an optical semiconductor device including the optical semiconductor element mounting substrate and an optical semiconductor element mounted on the optical semiconductor element mounting substrate.

  In still another aspect, the present invention relates to a method for manufacturing an optical semiconductor element mounting substrate having a concave portion having a bottom surface and a wall surface. The manufacturing method according to the present invention includes a step of forming at least a part of the wall surface of the concave portion by transfer molding using the silicone resin tablet.

  Advantageous Effects of Invention According to the present invention, it is possible to provide a silicone resin tablet which is hardly deformed and has excellent transportability and automatic transportability, a substrate for mounting an optical semiconductor element using the same, a method for manufacturing the same, and an optical semiconductor device. . In addition, a molded article having excellent optical properties, heat resistance and light resistance can be produced by transfer molding using the silicone resin tablet.

It is a perspective view showing one embodiment of a substrate for mounting an optical semiconductor element. It is the schematic which shows one Embodiment of the process of manufacturing the board | substrate for mounting an optical semiconductor element. It is a perspective view showing one embodiment of the state where an optical semiconductor element is mounted on a substrate for mounting an optical semiconductor element. FIG. 2 is a schematic cross-sectional view showing one embodiment of the optical semiconductor device. It is a schematic cross section showing other embodiments of an optical semiconductor device. It is a schematic cross section showing other embodiments of an optical semiconductor device. It is a schematic cross section showing one embodiment of a copper clad laminate. It is a schematic cross section which shows an example of the optical semiconductor device manufactured using the copper clad laminated board. It is a schematic cross section showing other embodiments of an optical semiconductor device.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[Silicone resin tablet]
By increasing the hardness, the silicone resin tablet of the present embodiment is less likely to be deformed, and is excellent in transportability and automatic transportability.

  The type A durometer hardness of the silicone resin tablet is preferably 50 or more. Improving the hardness of the silicone resin tablet tends to facilitate the handling of the tablet during automatic conveyance.

  The silicone resin tablet of the present embodiment can include a silicone resin containing a specific silicone resin (hereinafter, sometimes referred to as silicone resin (X)) and a pigment. The silicone resin (X) is preferably a silicone resin that is solid at 25 ° C. When the silicone resin tablet contains a solid silicone resin at 25 ° C., the hardness tends to be improved. By using a silicone resin that is liquid at 25 ° C. together with a silicone resin that is solid at 25 ° C., the pigment can be easily and uniformly mixed, and the tablet to be formed has excellent transportability.

  Further, the silicone resin (X) is a silicone resin in which the ratio of an aryl group or a cycloalkyl group bonded to a silicon atom is 20 mol% or more based on the total amount of the hydrocarbon group bonded to the silicon atom. It may be. By including a silicone resin having a high proportion of a bulky group such as an aryl group or a cycloalkyl group, the hardness of the silicone resin tablet tends to be improved.

Further, the silicone resin (X) is derived from Q and T when the silicon-containing bonding units Q, T and D are defined as follows in a solid-state ²⁹ Si-NMR spectrum measured by the DD / MAS method. It may be a silicone resin in which the ratio Q + T: D of the signal area derived from D to the signal area derived from D is from 1: 0 to 1: 0.5. Here, Q represents a silicon-containing bonding unit having four oxygen atoms bonded to one silicon atom, and T represents three oxygen atoms bonded to one silicon atom and a hydrogen atom or monovalent. Represents a silicon-containing bonding unit having one organic group, and D represents a silicon-containing bonding unit having two oxygen atoms bonded to one silicon atom and two hydrogen atoms or monovalent organic groups. Represent. By including a silicone resin having a high ratio of Q and T, the hardness of the silicone resin tablet tends to be improved.

  The silicone resin tablet can be produced by molding a silicone resin composition containing a silicone resin and a pigment into a tablet. Hereinafter, each component contained in the silicone resin composition constituting the silicone resin tablet of the present embodiment will be described.

(Silicone resin)
The silicone resin according to the present embodiment can take a form containing the silicone resin (X), and the silicone resin (X) is preferably a silicone resin that is solid at 25 ° C. In the present specification, a solid at 25 ° C refers to a substance having a softening point exceeding 25 ° C. The softening point of the silicone resin is determined, for example, by using a TMA-120 (manufactured by Seiko Instruments Inc., product name) as a measuring device, setting the measurement mode to Penetration (needle insertion mode), and increasing the temperature at a rate of 10 ° C./min. And a load of 98.1 mN (10 gf).

  The softening point of the silicone resin (X) is not particularly limited as long as it is higher than 25 ° C, but is preferably higher than 25 ° C and 180 ° C or lower, more preferably 26 ° C or higher and 150 ° C or lower. Within this range, handling when used for transfer molding tends to be easier.

  As the silicone resin (X), a silicone resin having an organic group having 1 to 12 carbon atoms bonded to a silicon atom is preferable, and a silicone resin having an organic group having 1 to 8 carbon atoms bonded to a silicon atom is more preferable. . The organic group is preferably a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include a benzyl group. Examples of the aryl group include a phenyl group, a tolyl group and a xylyl group. These groups may be halogenated hydrocarbon groups in which a hydrogen atom is partially substituted with a chlorine atom, a fluorine atom, or the like. As the organic group, an aryl group is preferred, and a phenyl group is more preferred, from the viewpoints of ease of synthesis of the silicone resin and easy formation of a solid at 25 ° C.

  From the viewpoint of improving transfer moldability, the silicone resin (X) may be a thermosetting silicone resin. Examples of the thermosetting silicone resin include a silicon compound having a group capable of performing an addition reaction.

  Examples of the group capable of performing the addition reaction include an alkenyl group, an alkynyl group, a carbonyl group, a thiol group, an epoxy group, an amino group, a sulfide group, and a hydrogen atom (Si-H) bonded to a silicon atom. Among these groups, a silicon compound having a hydrogen atom bonded to an alkenyl group and / or a silicon atom, that is, a silicon compound having a group capable of hydrosilylation is preferable.

Silicone resin (X) ^may as having a unit represented by R _{1 SiO ^3/2,} and unit represented by R _{1 SiO ^3/2,} units represented by R _{2 SiO 2/2} , R ³ SiO _1/2 and at least one unit selected from units represented by SiO _4/2 .

R ¹ , R ² and R ³ each independently represent a monovalent organic group, and is preferably a hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group are the same as those described above.

From the viewpoint of ease of synthesis of the silicone resin, R ¹ , R ² and R ³ are preferably each independently an alkyl group or an aryl group, more preferably a methyl group or a phenyl group.

  From the viewpoint of increasing the softening point of the silicone resin, a silicone resin having an aryl group or a cycloalkyl group is preferable, and from the viewpoint of industrial availability of raw materials, a silicone resin having a phenyl group is preferable.

  In the silicone resin (X) according to the present embodiment, the ratio of the aryl group or the cycloalkyl group bonded to the silicon atom is 20 mol% or more based on the total amount of the hydrocarbon group bonded to the silicon atom. It may be a silicone resin.

The content ratio of the aryl group or cycloalkyl group present in the silicone resin can be calculated by measuring the ¹ H-NMR spectrum of the silicone resin. Specifically, it is calculated from the ratio of the signal area derived from the aryl group or cycloalkyl group bonded to the silicon atom and the signal area derived from the linear alkyl group bonded to the silicon atom. Can be.

  The content ratio of the aryl group or the cycloalkyl group in the silicone resin (X) is preferably at least 20 mol%, more preferably at least 30 mol%, even more preferably at least 50 mol%. By setting the content ratio of the aryl group or the cycloalkyl group to 20 mol% or more, it becomes easy to obtain a silicone resin tablet whose shape is hardly deformed.

In the silicone resin (X) according to the present embodiment, when the silicon-containing bonding units Q, T, and D are defined as follows in a solid-state ²⁹ Si-NMR spectrum measured using the following DD / MAS method, And a silicone resin in which the ratio Q + T: D of the signal area derived from T to the signal area derived from D is 1: 0 to 1: 0.5.

  That is, Q represents a silicon-containing bonding unit having four oxygen atoms bonded to one silicon atom, and T represents three oxygen atoms bonded to one silicon atom and a hydrogen atom or monovalent. D represents a silicon-containing bonding unit having one organic group, and D represents a silicon-containing bonding unit having two oxygen atoms bonded to one silicon atom and two hydrogen atoms or two monovalent organic groups. . In addition, R in a formula respectively independently represents a monovalent organic group.

  The “oxygen atom” in Q, T, and D is an oxygen atom that mainly bonds between two silicon atoms. For example, an oxygen atom of a hydroxyl group that is bonded to a silicon atom may be considered. Further, the “organic group” is a monovalent organic group in which an atom bonded to a silicon atom is a carbon atom, and examples thereof include an organic group having 1 to 10 carbon atoms. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an N-aryl-substituted aminoalkyl group.

  The signal area ratio may be such that Q + T: D is 1: 0 to 1: 0.5, but from the viewpoint of obtaining a silicone resin tablet having higher hardness, Q + T: D is 1: 0 to 1: 0.3. And 1: 0 to 1: 0.2, or 1: 0 to 1: 0.1. When the signal area ratio is 1: 0.5 or less, it becomes easy to obtain a tablet having excellent automatic transportability.

The method of measuring solid-state ²⁹ Si-NMR for confirming the signal area ratio is not particularly limited, and includes, for example, the CP / MAS method and the DD / MAS method. The MAS method is adopted.

Incidentally, Roychen Joseph et al., Macromolecules, 1996, 29, p. 1305-1312, report the structural analysis of a composite of colloidal silica and polymethyl methacrylate using solid-state ²⁹ Si-NMR. Also, Aramata et al., BUNSEKI KAGAKU, 1998, 47, pp. 147-64. 971-978, report a silica-siloxane interface analysis in silicone rubber using solid-state ²⁹ Si-NMR. For the measurement of the solid-state ²⁹ Si-NMR spectrum, these reports can be appropriately referred to.

The chemical shifts of the silicon-containing bonding units Q, T, and D in the solid-state ²⁹ Si-NMR spectrum are respectively in the range of Q unit: -90 to -120 ppm, T unit: -45 to -80 ppm, and D unit: 0 to -40 ppm. As observed, it is possible to separate the signals of the silicon-containing bonding units Q, T and D and calculate the signal area derived from each unit. At the time of spectral analysis, an exponential function can be used as a Window function and the Line Broadening coefficient can be set in a range of 0 to 50 Hz from the viewpoint of improving analysis accuracy.

  The signal area can be calculated using general spectrum analysis software (for example, NMR software “TopSpin” (registered trademark) manufactured by Bruker).

  The number average molecular weight (Mn) of the silicone resin (X) is preferably less than 3000, more preferably less than 2000, and even more preferably less than 1500 from the viewpoint of fluidity during transfer molding. Mn of the silicone resin (X) may be 700 or more.

  The number average molecular weight (Mn) refers to a value measured using a calibration curve with standard polystyrene according to a gel permeation chromatography (GPC) method. Specifically, as a GPC measuring device, a pump (model L-6200 manufactured by Hitachi, Ltd.), a column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, product name), a detector (Hitachi, Ltd.) M-3 can be measured at a temperature of 30 ° C. and a flow rate of 1.0 mL / min using tetrahydrofuran as an eluent.

  The silicone resin according to the present embodiment can further contain a thermosetting silicone resin that is liquid at 25 ° C. together with the above-described silicone resin (X). As the thermosetting silicone resin liquid at 25 ° C., for example, a resin having a thermosetting functional group such as an alkenyl group and a SiH group (a group having a hydrogen atom bonded to a silicon atom) can be used. Si of the SiH group may be a silicon atom in the siloxane skeleton.

  From the viewpoint of improving the curability of the cured product, as a thermosetting silicone resin, a silicone compound having two or more alkenyl groups bonded to a silicon atom in one molecule, and a hydrogen atom bonded to a silicon atom in one molecule A silicone resin obtained by reacting two or more silicone compounds with each other may be used. A thermosetting silicone resin is a silicone compound having two or more alkenyl groups bonded to a silicon atom and two or more hydrogen atoms capable of reacting with an alkenyl group bonded to a silicon atom in one molecule. There may be.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a petenyl group, and a hexenyl group. Among them, a vinyl group is preferable. The alkenyl group may be bonded to a silicon atom at the terminal of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain, but from the viewpoint of the curing rate of the silicone resin composition, physical properties of the cured product, particularly strength. And may be bonded to silicon atoms at both ends of the molecular chain.

  Organic groups other than alkenyl groups may be bonded to silicon atoms in the thermosetting silicone resin liquid at 25 ° C. Examples of the organic group include an alkyl group such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; and an aryl group such as a phenyl group, a tolyl group, and a xylyl group. The organic group may be a halogenated hydrocarbon group in which a hydrogen atom of an alkyl group, a cycloalkyl group or an aryl group is partially substituted with a chlorine atom, a fluorine atom, or the like. The organic group other than the alkenyl group is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group, from the viewpoint of ease of synthesis of the thermosetting silicone resin. From the viewpoint of improving adhesiveness, the thermosetting silicone resin may further have a functional group such as an epoxy group and a thiol group.

  From the viewpoint of improving the curability during transfer molding, the thermosetting silicone resin liquid at 25 ° C. has 0.5 to 4.0 SiH groups per one alkenyl group present in one molecule. It is more preferable that the number is 1.0 to 3.0. When the number of SiH groups is in the above range, the curability of the silicone resin composition is more easily improved.

  The reactive group equivalent containing the alkenyl group and the SiH group of the thermosetting silicone resin liquid at 25 ° C. is preferably 200 to 2000 g / mol, more preferably 200 to 1500 g / mol, and more preferably 200 to 1000 g / mol. More preferably, it is mol. When the reactive group equivalent of the thermosetting silicone resin is 2000 g / mol or less, the hardness of the cured product tends to be more difficult to decrease. As the reactive group equivalent, a theoretical value obtained by calculating from the charged composition at the time of synthesizing the thermosetting silicone resin can be adopted, and the calculation method is to calculate the molecular weight of the theoretical average molecular structure / the number of theoretical reactive groups. Can be obtained by:

  The viscosity of the thermosetting silicone resin liquid at 25 ° C. is preferably 1 Pa · s or more, more preferably 3 Pa · s or more at 25 ° C., from the viewpoint of being able to mix uniformly with the pigment and obtaining good workability. It is preferable that the viscosity of the silicone resin is 10 Pa · s or less. The above viscosity is measured by Research Equipment (London) LTD. It can be measured using an ICI cone plate type viscometer manufactured by Toshiba Corporation.

  As the thermosetting silicone resin liquid at 25 ° C., the handleability and transfer moldability at the time of mixing with a pigment or the like are better, and the hardness of the silicone resin composition after curing is higher, Preferably, the Mn is less than 3000, more preferably less than 2000, even more preferably less than 1500. Mn of the thermosetting silicone resin liquid at 25 ° C. may be 1200 or more.

  As the thermosetting silicone resin liquid at 25 ° C., silicone compounds such as polyorganosiloxane, polyorganosilsesquioxane, polyorganohydrogensiloxane, and polyorganoshydrogensilsesquioxane can be used. These silicone compounds can be synthesized using a known method.

  For example, polymethylsilsesquioxane can be synthesized by adding methyltrichlorosilane to a ketone or ether solvent in the presence of an amine, adding water dropwise at a low temperature, and condensing by hydrolysis. Further, an alkali metal carboxylate and an alcohol are dissolved in a mixed solution forming a two-layer of water and an organic solvent, and methyltrichlorosilane is dropped into the system, which is condensed by hydrolysis to obtain polymethyl Silsesquioxane can be synthesized. Polyphenylsilsesquioxane hydrolyzes phenyltrichlorosilane to obtain a prepolymer or phenylsilanetriol, and further removes water generated in the presence of a basic catalyst in a toluene solvent by azeotropic distillation. It can be synthesized by condensation. In addition, an alkali metal carboxylate and a lower aliphatic alcohol are dissolved in a mixed solution forming a two-layer of water and an organic solvent, and phenyltrichlorosilane is dropped into this system, and the mixture is hydrolyzed to obtain polyphenylsilsesquicene. Oxane can be synthesized. Further, a prepolymer obtained by hydrolyzing methyltriethoxysilane, phenyltrimethoxysilane and vinyltrimethoxysilane in the presence of an acidic catalyst is further reacted in an isopropyl alcohol solvent in the presence of a basic catalyst to obtain a polymer. It is possible to synthesize methylphenylvinylsilsesquioxane.

  When the silicone resin contains a thermosetting silicone resin which is liquid at 25 ° C. together with the silicone resin (X), it is easy to obtain a silicone resin tablet which is excellent in automatic transportability. Is preferably at least 5 parts by mass, more preferably at least 10 parts by mass, even more preferably at least 20 parts by mass, based on 100 parts by mass of the thermosetting silicone resin liquid at 25 ° C. On the other hand, from the viewpoint of improving the curability of the silicone resin composition during transfer molding, the content of the silicone resin (X) is 40 parts by mass or less based on 100 parts by mass of the liquid thermosetting silicone resin at 25 ° C. And more preferably 30 parts by mass or less. That is, the content of the silicone resin (X) contained in the silicone resin can be 5 to 40 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of the thermosetting silicone resin liquid at 25 ° C. And 20 to 30 parts by mass.

  From the viewpoint of further improving the automatic transportability, the total amount of the silicone resin component contained in the silicone resin composition is preferably 0.1% by mass or more, based on the total amount of components that become solids after curing of the silicone resin composition. And more preferably 3% by mass or more, and further preferably 5% by mass or more. From the viewpoint of the mechanical strength of the cured product, the total amount of the silicone resin components contained in the silicone resin composition is preferably 40% by mass or less, based on the total amount of components that become solids after curing of the silicone resin composition. It is more preferably at most 20% by mass, more preferably at most 20% by mass. That is, the total amount of the silicone resin component contained in the silicone resin composition can be 0.1 to 40% by mass, based on the total amount of the component which becomes a solid after curing of the silicone resin composition, and can be 3 to 30% by mass. %, Or 5 to 20% by mass.

(Curing catalyst)
The silicone resin composition according to the present embodiment can contain a curing catalyst. That is, the silicone resin tablet of the present embodiment can include a curing catalyst. Although the curing catalyst according to the present embodiment is not particularly limited, it can be appropriately selected according to the type of curing reaction (hydrosilylation reaction, condensation reaction, and the like) of the silicone resin, and a catalyst having a catalytic activity for accelerating the reaction can be used. Examples of the curing catalyst for the hydrosilylation reaction include, for example, Karstedt's catalyst, platinum alone, alumina, silica, carbon black or the like with solid platinum supported thereon, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And platinum-olefin complexes, platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, and dicarbonyldichloroplatinum. These curing catalysts may be used alone or in combination of two or more.

Examples of the platinum-olefin complex include Pt (CH ₂ ＣＨCH ₂ ) ₂ (PPh ₃ ) ₂ and Pt (CH ₂ ＣＨCH ₂ ) ₂ Cl ₂ . Examples of the platinum-vinylsiloxane complex include platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex, platinum- (ViMe ₂ SiOSiMe ₂ Vi) _n and platinum -[(MeViSiO) ₄ ] _m . Platinum - The phosphine complexes, such as platinum - _{(PPh 3) 4} and platinum - _{(PBu 3) 4)} and the like. Examples of the platinum-phosphite complex include platinum- [P (OPh) ₃ ] ₄ and platinum [P (OBu) ₃ ] ₄ . In the above formula, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m each represent an integer.

  Among these curing catalysts, chloroplatinic acid, a platinum-olefin complex or a platinum-vinylsiloxane complex is preferable from the viewpoint of catalytic activity.

  On the other hand, as a curing catalyst for the condensation reaction, for example, an organic metal catalyst such as an organic acid zinc, a Lewis acid catalyst, an organic aluminum compound and an organic titanium compound can be used. As the organic metal catalyst, for example, zinc octylate, zinc benzoate, zinc p-tert-butyl benzoate, zinc laurate, zinc aluminum stearate, aluminum perchlorate, aluminum phosphate, aluminum triisopropoxide, Examples include aluminum acetylacetonate, ethyl acetoacetate aluminum di (normal butyrate), aluminum-n-butoxydiethylacetoacetate, tetrabutyl titanate, tetraisopropyl titanate, tin octylate, cobalt naphthenate, and tin naphthenate.

  The amount of the curing catalyst contained in the silicone resin composition (silicone resin tablet) is not particularly limited. However, from the viewpoint of improving the curability of the silicone resin tablet during transfer molding, the amount is preferably 0.1 to 100 parts by mass of the silicone resin. The amount is preferably from 0.01 to 0.5 part by mass, more preferably from 0.01 to 0.3 part by mass, and still more preferably from 0.01 to 0.2 part by mass.

(Pigment)
The pigment according to the present embodiment can be selected according to the purpose of use of the cured product formed using the silicone resin tablet. For example, when high light reflectivity is required for the cured product, a white pigment can be used as the pigment, and when the optical semiconductor device is required to be black when the light emitting element does not emit light, a black pigment is used as the pigment. Can be used. Examples of the pigment include a white pigment, a black pigment, a red pigment, a yellow pigment, an orange pigment, a violet (violet) pigment, a blue pigment, and a green pigment. The pigment may be an azo pigment, a lake pigment or a fluorescent pigment.

  Examples of the black pigment include carbon black. Red pigments include, for example, lead red, iron oxide red, quinacridone, diketopyrrolopyrrole, anthraquinone, perylene, perinone, and indigoid. Examples of the yellow pigment include, for example, graphite and zinc yellow. Examples of the blue pigment include ultramarine blue, prussian blue (potassium ferrocyanide), phthalocyanine blue, anthraquinone, and indigoid. Orange pigments include, for example, diketopyrrolopyrrole, perylene, anthraquinone, perinone, quinacridone, and indigoid. Examples of purple (violet) pigments include dioxazine, quinacridone, perylene, indigoid, anthraquinone, and xanthene. Examples of the green pigment include phthalocyanine, azomethine, and perylene. These pigments may be used alone or in combination of two or more.

  Examples of the white pigment include titanium oxide, zinc oxide, aluminum oxide (alumina), magnesium oxide, antimony oxide, zirconium oxide, and inorganic hollow particles. These may be used alone or in combination of two or more.

  The inorganic hollow particles are particles formed from a material other than titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide, and zirconium oxide. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, and particles of shirasu.

  When a cured product requires light reflection properties, it is preferable to use a white pigment as the pigment. When the silicone resin composition contains a white pigment, the molded silicone resin tablet becomes white, and the cured product has excellent light reflectance. Therefore, when the molded body is used as a light reflecting member provided on the optical semiconductor element mounting substrate, a high-brightness optical semiconductor device can be obtained. From the viewpoint of further improving the light reflection characteristics of the cured product, it is more preferable to use titanium oxide as the white pigment.

When using a white pigment, the center particle size of the white pigment is not particularly limited, but is preferably in the range of 0.1 to 50 μm, more preferably in the range of 0.1 to 30 μm, and more preferably in the range of 0.1 to 10 μm. More preferably, it is within the range. When the central particle size of the white pigment is 0.1 μm or more, the particles are less likely to aggregate and the dispersibility tends to be further improved, and when it is 50 μm or less, the light reflection characteristics of the cured product tend to be more easily obtained. . The center particle diameter can be determined as a mass average value D ₅₀ (or median diameter) in a particle size distribution measurement by a laser light diffraction method.

  When a white pigment is used, the content of the pigment in the silicone resin composition is preferably in the range of 10 to 90% by volume, more preferably 10 to 85% by volume, based on the total amount of the silicone resin composition. preferable. When the content of the pigment is 10% by volume or more, the optical properties of the cured product are easily obtained, and when the content is 90% by volume or less, the moldability of the silicone resin composition is easily improved, and the substrate for mounting an optical semiconductor element is provided. Is easy to manufacture.

  When a white pigment is used, the content of the pigment in the silicone resin composition (silicone resin tablet) should be 1% by mass or more based on the total amount of the silicone resin composition since the optical characteristics of the cured product are easily obtained. , And more preferably 10% by mass or more. On the other hand, the content of the pigment is preferably 97% by mass or less, and more preferably 50% by mass or less, since the moldability of the silicone resin composition is easily improved and the substrate for mounting an optical semiconductor element is easily produced. Is more preferable. That is, the content of the pigment in the silicone resin composition (silicone resin tablet) can be in the range of 1 to 97% by mass based on the total amount of the silicone resin composition, and even in the range of 10 to 50% by mass. Good.

(Other components)
The silicone resin composition may further contain various additives such as an inorganic filler, an antioxidant, a release agent, a dispersant, and an ion scavenger, in addition to the components described above. That is, the silicone resin tablet may further include various additives such as an inorganic filler, an antioxidant, a release agent, a dispersant, and an ion scavenger.

  The inorganic filler has, for example, an effect of increasing the strength and hardness of a cured product obtained from the silicone resin composition and reducing the coefficient of linear expansion. Examples of the inorganic filler include fused spherical silica, crushed silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. The center particle diameter of the inorganic filler is preferably in the range of 1 to 100 μm from the viewpoint of improving the packing efficiency with the pigment. The content of the inorganic filler in the silicone resin composition is preferably in the range of 5 to 75% by volume, based on the total amount of components that become solid after curing of the silicone resin composition. In the present specification, a substance having both effects of a pigment and an inorganic filler belongs to a pigment in principle. However, when the silicone resin composition contains two or more kinds of substances having both effects of the pigment and the inorganic filler, one of the substances belongs to the inorganic filler. As the substance belonging to the inorganic filler, a substance other than the substances exemplified as the above-mentioned pigments is prioritized.

  From the viewpoint of improving the strength and hardness of the cured product, the total amount of the pigment and the inorganic filler contained in the silicone resin composition (silicone resin tablet) is in the range of 10 to 90% by mass based on the total amount of the silicone resin composition. It is preferably present, more preferably in the range of 20 to 87% by mass, and even more preferably in the range of 40 to 80% by mass. The ratio of the pigment to the total amount of the pigment and the inorganic filler can be appropriately determined according to the purpose of use of the cured product, the type of the pigment, and the like.

  A coupling agent or the like may be added to the silicone resin composition as needed. That is, the silicone resin tablet can include a coupling agent and the like. In this case, the interfacial adhesion between the silicone resin and inorganic components such as pigments and inorganic fillers can be improved. Examples of the coupling agent include a silane coupling agent and a titanate coupling agent. As the silane coupling agent, generally known compounds such as epoxy silane, amino silane, cationic silane, vinyl silane, acryl silane, and mercapto silane can be used. The coupling agent may be a composite system of the above silane coupling agent. The amount of the coupling agent used is preferably adjusted as appropriate in consideration of the amount of the surface coating on the pigment.However, from the viewpoint of improving the interfacial adhesion and the curability, the amount is preferably 0% based on the total amount of the silicone resin composition. 0.01% by mass or more, preferably 5% by mass or less. Inorganic components such as pigments and inorganic fillers may be previously treated with the coupling agent.

  A curing retarder may be added to the silicone resin composition for the purpose of improving storage stability or adjusting the reactivity of the hydrosilylation reaction in the production process. That is, the silicone resin tablet can include a cure retarder. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, and maleic esters. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide, and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like.

  Among these curing retarders, those having good retarding activity and being colorless or relatively non-colored such as pale yellow are preferred. The curing retarders may be used alone or in combination of two or more.

  The addition amount of the curing retarder is preferably in the range of 0.1 to 10000 mol, and more preferably in the range of 1 to 50 mol, per 1 mol of the curing catalyst used.

  For the purpose of modifying the properties, it is possible to add a thermosetting resin other than the silicone resin to the silicone resin composition within a range that does not adversely affect the properties. That is, the silicone resin tablet may include a thermosetting resin other than the silicone resin. Examples of the thermosetting resin include, but are not limited to, an epoxy resin, an acrylic resin, a cyanate resin, a phenol resin, a polyimide resin, a polyamideimide resin, and a urethane resin. Among these, epoxy resins are preferred from the viewpoint of high convenience as electronic components and excellent adhesiveness with metal components. The thermosetting resin is preferably a colorless or relatively uncolored resin such as pale yellow.

  Although it does not specifically limit as an epoxy resin, For example, hexafluorobisphenol A type diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis (4-glycidyloxycyclohexyl) propane , 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane)- 1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate and di Include the Lil monoglycidyl isocyanurate. When using an epoxy resin, as an epoxy resin curing agent, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, hydrogenated methylnadic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. An acid anhydride-based curing agent; aliphatic acids such as 1,4-cyclohexanedicarboxylic acid or anhydrides thereof may be further added. These epoxy resins or epoxy resin curing agents may be used alone or in combination of two or more.

  When a silicone resin tablet formed from the silicone resin composition is used as a light reflecting material, the cured product preferably has a light reflectance of 80% or more in the entire wavelength range of 440 to 700 nm. When the light reflectivity is 80% or more, there is a tendency that the luminance can be further contributed to the improvement of the optical semiconductor device. In order to further improve the brightness of the optical semiconductor device, the light reflectance at a wavelength of 460 nm after curing is preferably 80% or more, and more preferably 90% or more. The light reflectance is a value obtained by preparing a cured product having a thickness of 3.0 mm and using an integrating sphere spectrophotometer.

  When a silicone resin tablet is used as the light reflecting material, from the viewpoint of improving the heat resistance coloring property, the light reflectance of the cured product is in a range of 440 to 800 nm after a heat resistance test in which the cured product is exposed to an environment of 150 ° C. for 1000 hours. It is preferably at least 80%. Further, at the time of measurement after the above-mentioned heat resistance test, the light reflectance at a wavelength of 460 nm is preferably 85% or more, more preferably 90% or more. The light reflection properties of such a silicone resin tablet can be realized by appropriately adjusting the amounts of the various components constituting the silicone resin composition, and more specifically, for example, a colorless thermosetting resin This can be achieved by highly filling the component and a white pigment having a high refractive index. The light reflectance is a value obtained by preparing a cured product having a thickness of 3.0 mm and using an integrating sphere spectrophotometer.

  The silicone resin composition can be prepared by uniformly dispersing and mixing the various components exemplified above. The mixing means, mixing conditions and the like are not particularly limited, but are preferably such means and conditions as to obtain a powdery silicone resin composition. As a preparation method, for example, various components are kneaded using a device such as a mixing roll, an extruder, a kneader, a roll, an extruder, a raiger, a stirring and mixing device that combines rotation and revolution, and then the obtained kneading is performed. There is a method of pulverizing an object. Before kneading, the obtained kneaded material may be cooled. The type of kneading is not particularly limited, but is preferably kneading. The conditions at the time of melt-kneading may be appropriately determined depending on the types or amounts of various components used, and are not particularly limited. For example, from the viewpoint of further suppressing excessive chemical reaction during heating, the reaction may be performed at a room temperature of 15 to 30 ° C, or may be performed at a temperature range of 30 to 100 ° C for 5 to 40 minutes. It may be carried out in a temperature range of 100 ° C. for 10 to 30 minutes. When the temperature of the melt-kneading is 30 ° C. or higher, various components can be more sufficiently melt-kneaded, and the dispersibility tends to be further improved. On the other hand, when the melt-kneading is performed at 100 ° C. or lower, the increase in the molecular weight of the resin composition can be further suppressed, and the curing of the resin composition before forming a molded article such as a substrate can be further suppressed. Further, when the melt-kneading time is 5 minutes or more, it is possible to further suppress the resin from oozing out of the mold at the time of molding the substrate or the like, and when it is within 40 minutes, it is possible to further suppress the polymerization of the resin composition. In addition, curing of the resin composition before molding can be further suppressed.

  The silicone resin tablet of the present embodiment can be manufactured using the above-described silicone resin composition. The tablet molding conditions are not particularly limited. For example, a silicone resin tablet can be obtained by pressure molding at room temperature under the conditions of about 0.5 to 60 MPa and about 1 to 15 seconds.

  In addition, the tablet in this specification means a solid composition that maintains a constant shape at room temperature and does not substantially change in shape over time. The shape of the tablet according to the present embodiment is not particularly limited, and includes a columnar shape, a prismatic shape, a disk shape, a spherical shape, and the like, but is preferably a general cylindrical shape for transfer molding.

  The silicone resin tablet of the present embodiment preferably has a type A durometer hardness of 50 or more, more preferably 55 or more, and even more preferably 60 or more. When the hardness is 50 or more, the tablet is hardly deformed, and the handling property is further improved. Therefore, automatic conveyance by a machine becomes possible without any problem, and when the hardness is higher, the reliability tends to be improved. Since the hardness of the silicone resin tablet is preferably as high as possible, the upper limit of the type A durometer hardness is not particularly limited, but may be about 100. The type A durometer hardness is preferably a value measured after the tablet was allowed to stand at 25 ° C. for 3 minutes.

  The type A durometer hardness can be measured according to the method described in JIS: K6253. In the present specification, a value obtained by pressing a needle of a type A durometer against a thermosetting resin tablet and reading a value after one minute is defined as hardness.

  From the viewpoint of reducing the surface tackiness, the surface of the silicone resin tablet may be coated with a filler. The inorganic filler used for coating is not particularly limited, and examples thereof include the same inorganic fillers that can be contained in the silicone resin composition.

  There is no particular limitation on the method of coating the adherend with the filler as long as it can contact the silicone resin tablet. For example, there is a method in which a filler is placed in a container or a bag and the silicone resin tablet is coated with the filler by vibration using a machine, and a method in which the filler is manually sprinkled.

(Cured product)
The cured product of the present embodiment is obtained by thermally curing the above-described silicone resin composition or silicone resin tablet. The conditions of the thermal curing are not particularly limited, but for example, curing can be performed by heating at a temperature of 170 to 200 ° C. for 60 to 300 seconds. The thermosetting may be performed as one of the steps included in the molding method described below.

(Molded body)
The molded article of the present embodiment is obtained by thermosetting and molding using the above-mentioned silicone resin composition or silicone resin tablet by a molding method such as compression molding, transfer molding, injection molding, or injection compression molding. That is, in the present embodiment, the “molded body” refers to a cured product that is cured in a state where the molded article has a desired shape.

(Substrate for mounting optical semiconductor elements)
The optical semiconductor element mounting substrate according to the present embodiment has a concave portion composed of a bottom surface and a wall surface. The bottom surface of the concave portion is an optical semiconductor element mounting portion (optical semiconductor element mounting region), and the wall surface of the concave portion, that is, at least a part of the inner peripheral side surface of the concave portion is formed of a molded article formed from the silicone resin tablet of the present embodiment. It is.

  FIG. 1 is a perspective view showing an embodiment of an optical semiconductor element mounting substrate. The optical semiconductor element mounting substrate 110 includes a metal wiring 105 (first connection terminal and second connection terminal) on which Ni / Ag plating 104 is formed, and a metal wiring 105 (first connection terminal and second connection). A metal wiring 105 on which Ni / Ag plating 104 is formed, and an insulating resin molded body 103 ′ and a reflector 103. An optical semiconductor element mounting area (recess) 200 is provided. The bottom surface of the concave portion 200 is composed of the metal wiring 105 on which the Ni / Ag plating 104 is formed and the insulating resin molded body 103 ′, and the wall surface of the concave portion 200 is composed of the reflector 103. The reflector 103 and the insulating resin molded body 103 'are molded bodies formed using the silicone resin tablet of the present embodiment.

  The method for manufacturing the optical semiconductor element mounting substrate is not particularly limited. For example, it can be manufactured by transfer molding using a silicone resin tablet. FIG. 2 is a schematic view illustrating one embodiment of a process of manufacturing an optical semiconductor element mounting substrate. The substrate for mounting an optical semiconductor element is formed by, for example, punching a metal foil, forming a metal wiring 105 by a known method such as etching, and applying Ni / Ag plating 104 by electroplating (FIG. 2A), The metal wiring 105 is placed in a mold 151 having a predetermined shape, and a silicone resin tablet, which may be heated to increase the fluidity, is injected from the resin injection port 150 of the mold 151, and is subjected to transfer molding under predetermined conditions. It can be manufactured through a process (FIG. 2 (b)) and a process of removing the mold 151 (FIG. 2 (c)). In order to perform transfer molding efficiently, an apparatus provided with a mechanism in which a silicone resin tablet is supplied to a pod provided in a mold using an automatic transfer device and transfer molding is started can be used.

  In this manner, the optical semiconductor element mounting area (recess) 200 surrounded by the reflector 103 made of a cured product of the silicone resin tablet is formed on the optical semiconductor element mounting substrate. In addition, the bottom surface of the concave portion 200 is composed of a metal wiring 105 serving as a first connection terminal and a second connection terminal, and an insulating resin molded body 103 ′ provided between the metal wiring 105 and the cured product of the silicone resin tablet. Is done. The transfer molding conditions are preferably a mold temperature of 170 to 200 ° C., a molding pressure of 0.5 to 20 MPa, 60 to 300 seconds, and an after cure temperature of 120 to 180 ° C. for 1 to 3 hours. . The mold temperature is more preferably from 150 to 190 ° C, and the molding pressure is more preferably from 2 to 8 MPa.

  The color of the reflector 103 is not limited and can be appropriately determined depending on the type of the pigment to be used, but is preferably white from the viewpoint of further increasing the light reflectance.

(Optical semiconductor device)
The optical semiconductor device according to the present embodiment has the optical semiconductor element mounting substrate and the optical semiconductor element mounted on the optical semiconductor element mounting substrate. As a more specific example, the optical semiconductor element mounting substrate, an optical semiconductor element provided in a concave portion of the optical semiconductor element mounting substrate, and a phosphor-containing seal for filling the concave portion and sealing the optical semiconductor element. An optical semiconductor device including a resin stopper.

  FIG. 3 is a perspective view illustrating an embodiment in which the optical semiconductor element 100 is mounted on the optical semiconductor element mounting substrate 110. As shown in FIG. 3, the optical semiconductor element 100 is mounted at a predetermined position in an optical semiconductor element mounting area (recess) 200 of the optical semiconductor element mounting substrate 110, and is electrically connected to a metal wiring 105 by a bonding wire 102. You. 4 and 5 are schematic sectional views showing one embodiment of the optical semiconductor device. As shown in FIGS. 4 and 5, the optical semiconductor device includes an optical semiconductor element mounting substrate 110, an optical semiconductor element 100 provided at a predetermined position in the concave portion 200 of the optical semiconductor element mounting substrate 110, and a concave portion 200. And a sealing resin portion made of a transparent sealing resin 101 including a phosphor 106 for sealing the optical semiconductor element by filling the optical semiconductor element with the optical semiconductor element 100 and the metal wiring 105 on which the Ni / Ag plating 104 is formed. Are electrically connected by the bonding wire 102 or the solder bump 107.

  FIG. 6 is also a schematic sectional view showing an embodiment of the optical semiconductor device. In the optical semiconductor device shown in FIG. 6, an LED element 300 is arranged at a predetermined position on a lead 304 on which a reflector 303 is formed via a die bonding material 306, and the LED element 300 and the lead 304 are electrically connected by a bonding wire 301. The LED element 300 is connected and is sealed with the transparent sealing resin 302 including the phosphor 305.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to this. For example, when a white pigment is contained as a pigment, a molded article formed from the silicone resin tablet according to the present embodiment can be used as a light reflecting resin layer. As this embodiment, a copper-clad laminate, an optical semiconductor element mounting substrate, and an optical semiconductor element will be described.

  The copper clad laminate according to the present embodiment includes a resin layer formed using the above-described silicone resin tablet, and a copper foil laminated on the resin layer.

  FIG. 7 is a schematic sectional view showing a preferred embodiment of the copper-clad laminate. As shown in FIG. 7, the copper clad laminate 400 includes a base 401, a resin layer 402 stacked on the base 401, and a copper foil 403 stacked on the resin layer 402. Here, the resin layer 402 is formed using the above-described silicone resin tablet of the present embodiment.

  As the substrate 401, a substrate used for a copper-clad laminate can be used without any particular limitation, and examples thereof include a resin laminate such as an epoxy resin laminate and a substrate for mounting an optical semiconductor.

  The copper-clad laminate 400 can be produced, for example, by forming the resin layer 402 on the surface of the base material 401 using the silicone resin tablet according to the present embodiment, then superposing the copper foil 403, and applying heat and pressure.

  The conditions for the heating and pressurizing are not particularly limited, but, for example, it is preferable to perform the heating under the conditions of 130 to 180 ° C, 0.5 to 4 MPa, and 30 to 600 minutes.

  Using the copper-clad laminate, a printed wiring board for an optical member for mounting an LED or the like can be manufactured. The copper-clad laminate 400 shown in FIG. 7 has a resin layer 402 and a copper foil 403 laminated on one surface of a base material 401. And copper foil 403 may be laminated.

  FIG. 8 is a schematic cross-sectional view showing one example of an optical semiconductor device manufactured using a copper-clad laminate. As shown in FIG. 8, the optical semiconductor device 500 is a surface-mounted light emitting diode including an optical semiconductor element 410 and a transparent sealing resin 404 provided so as to seal the optical semiconductor element 410. is there. In the optical semiconductor device 500, the optical semiconductor element 410 is adhered to the copper foil 403 via the adhesive layer 408, and is electrically connected to the copper foil 403 by the bonding wire 409.

  Further, as another embodiment of the optical semiconductor element mounting substrate, an optical semiconductor element mounting substrate including a resin layer formed between a plurality of conductor members (connection terminals) on a substrate using the above-described silicone resin tablet. A substrate. In another embodiment of the optical semiconductor device, the optical semiconductor element is mounted on the optical semiconductor element mounting substrate.

  FIG. 9 is a schematic sectional view showing a preferred embodiment of the optical semiconductor device. As shown in FIG. 9, the optical semiconductor device 600 includes a base 601, a plurality of conductor members 602 formed on the surface of the base 601, and a resin formed between the plurality of conductor members (connection terminals) 602. A surface mounting type light emitting device in which an optical semiconductor element 610 is mounted on an optical semiconductor element mounting substrate having a layer 603 and a transparent sealing resin 604 is provided so as to seal the optical semiconductor element 610. It is a diode. In the optical semiconductor device 600, the optical semiconductor element 610 is adhered to the conductor member 602 via an adhesive layer 608, and is electrically connected to the conductor member 602 by a bonding wire 609. The resin layer 603 is formed using the above-described silicone resin tablet.

  As the substrate 601, a substrate used for a substrate for mounting an optical semiconductor element can be used without any particular limitation, and examples thereof include a resin laminate such as an epoxy resin laminate.

  The conductor member 602 functions as a connection terminal, and can be formed by a known method such as a method of photo-etching a copper foil.

  The substrate for mounting an optical semiconductor element can be manufactured by molding a resin layer 603 between a plurality of conductor members 602 on a substrate 601 using a silicone resin tablet.

  Thereafter, excess resin components adhering to the surface of the conductor member 602 are removed by buffing or the like to expose a circuit composed of the conductor member 602, thereby obtaining a substrate for mounting an optical semiconductor element.

  Further, in order to secure the adhesion between the resin layer 603 and the conductor member 602, the conductor member 602 may be subjected to a roughening treatment such as an oxidation-reduction treatment and a CZ treatment.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. The present invention can be implemented in various modes different from the above-described embodiment without departing from the gist thereof.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

<Method of measuring various properties of silicone resin>
First, methods for measuring various characteristics in the following synthesis examples are described below.

(1) Measurement of Softening Point The softening point of the silicone resin was measured using TMA-120 type (product name, manufactured by Seiko Instruments Inc.). The measurement conditions were as follows: measurement mode: Penetration (needle insertion mode), heating rate: 10 ° C./min, load: 98.1 mN (10 gf).

(2) Measurement of number average molecular weight (Mn) Mn of the silicone resin was used as a GPC measuring device by a pump (manufactured by Hitachi, Ltd., product name: L-6200) and a column (manufactured by Tosoh Corporation, product name: TSKgel-). G5000HXL and TSKgel-G2000HXL) and a detector (manufactured by Hitachi, Ltd., product name: L-3300RI). The measurement conditions used tetrahydrofuran as an eluent, the temperature was 30 ° C., and the flow rate was 1.0 mL / min.

(3) Measurement of Signal Area Ratio of Silicon-Containing Bonding Units Q, T, and D The signal area ratio of the silicon-containing bonding units Q, T, and D of the silicone resin was measured using a solid ²⁹ Si-NMR apparatus as “FT-NMR AV400WB”. (Manufactured by Bruker BioSpin Co., Ltd., product name). The measurement conditions were as follows: measurement mode: DD / MAS method, probe: 4 mmφ CPMAS probe, magnetic field: 9.4 T, resonance frequency: 79 Hz, MAS rotation speed: 6 kHz, delay time: 150 seconds. As a standard sample, sodium 3-trimethylsilylpropionate was used.

As a measurement sample, a finely pulverized silicone resin was packed in a ZrO ₂ rotor and attached to a probe for measurement. In the spectral analysis, the Line Broadening coefficient was set to 2 Hz, and the signal area ratio (Q + T: D) of the obtained silicon-containing bonding units Q, T, and D was determined.

(4) Measurement of aryl group or cycloalkyl group bonded to silicon atom
The content ratio of the aryl group or the cycloalkyl group in the silicone resin was measured using "FT-NMR AV400M" (product name, manufactured by Bruker BioSpin, Inc.) as a ¹ H-NMR apparatus. The measurement conditions were as follows: measurement mode: decoupling (qualitative mode), pulse width: 8.3 μm, delay time: 2 seconds. Tetramethylsilane was used as a standard sample.

<Synthesis of silicone resin>
(Synthesis example 1)
A solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of dimethylchlorosilane-polydimethylsiloxane at both ends and 8.5 g of methylvinyldichlorosilane in 200 g of toluene was slowly dropped into 1000 g of water so as not to generate excessive heat, and hydrolyzed. Next, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with an aqueous potassium hydroxide solution, and after azeotropic dehydration, a solvent such as toluene was distilled off to synthesize a silicone resin A1.
Next, a solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of dimethylchlorosilane-polydimethylsiloxane at both ends and 6.9 g of methyldichlorosilane in toluene was slowly dropped into 1000 g of water so as not to generate excessive heat, and hydrolyzed. Next, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with an aqueous potassium hydroxide solution, and after azeotropic dehydration, a solvent such as toluene was distilled off to obtain a silicone resin B1.
A mixture of silicone resins A1 and B1 at a mass ratio of 1: 1 was used as a thermosetting silicone resin.

(Synthesis example 2)
100 g of toluene, 40 μL of platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex (1.7% by mass of platinum), 10 g of triallyl isocyanurate and 1 g of 1 80 g of 3,3,5,7-tetramethylcyclotetrasiloxane was added to a 500 mL flask and stirred at 120 ° C. for 2 hours while refluxing. Next, toluene was distilled off under reduced pressure to obtain a colorless and transparent prepolymer. Then, 80 g of triallyl isocyanurate was added and mixed at 40 ° C. for 1 hour to obtain a liquid isocyanuric skeleton-containing silicone resin. Mn of the obtained isocyanuric skeleton-containing silicone resin was 1,800, and viscosity was 5 Pa · s.

(Synthesis example 3)
198.3 g of phenyltriethoxysilane, 24.8 g of isopropyl alcohol, 24.8 g of toluene, 0.28 g of concentrated hydrochloric acid and 36 g of distilled water were added to a 500 mL flask, and the mixture was stirred at 110 ° C. for 4 hours while refluxing. Next, the colorless solid silicone resin A was obtained by distilling off toluene under reduced pressure. The obtained silicone resin A had a softening point of 75 ° C., Mn of 790, an area ratio of Q + T: D of 1: 0, and a ratio of aryl groups bonded to silicon atoms of 100%. Was.

(Synthesis example 4)
89.2 g of methyltriethoxysilane, 99 g of phenyltriethoxysilane, 23.6 g of isopropyl alcohol, 23.6 g of toluene, 0.28 g of concentrated hydrochloric acid and 36 g of distilled water are added to a 500 mL flask, and the mixture is refluxed at 110 ° C. for 3 hours. Stirred. Next, the colorless solid silicone resin B was obtained by distilling off toluene under reduced pressure. The obtained silicone resin B has a softening point of 53 ° C., an Mn of 901, an area ratio of Q + T: D of 1: 0, and a ratio of aryl groups bonded to silicon atoms of 51%. Was.

(Synthesis example 5)
142.6 g of methyltriethoxysilane, 39.7 g of phenyltriethoxysilane, 22.8 g of isopropyl alcohol, 22.8 g of toluene, 0.28 g of concentrated hydrochloric acid and 36 g of distilled water are added to a 500 mL flask, and the mixture is heated at 110 ° C. for 2.5 hours. While stirring over reflux. Next, toluene was distilled off under reduced pressure to obtain a colorless solid silicone resin C. The obtained silicone resin C had a softening point of 29 ° C., an Mn of 1300, an area ratio of Q + T: D of 1: 0, and a ratio of aryl groups bonded to silicon atoms of 23%. Was.

<Preparation of silicone resin composition and preparation of silicone resin tablet>
(Examples 1 to 8)
Each component was blended according to the blending ratio (parts by mass) shown in Table 1, and the mixture was sufficiently kneaded and dispersed by a grinder to obtain a powdery silicone resin composition. Next, the obtained silicone resin composition is filled in a mold having a metal mold having a circular through-hole having a diameter of 13 mm as a die, and a silicone resin tablet is formed using a punch and a hand press. did. The weight per tablet was 5 g.

(Comparative Examples 1 to 3)
Each component was blended according to the blending ratio (parts by mass) shown in Table 2, and sufficiently kneaded and dispersed by a grinder to obtain a paste-like or clay-like kneaded material. Since the silicone resin compositions of Comparative Examples 1 and 2 were in paste form, tablets could not be produced. Although the silicone resin composition of Comparative Example 3 was clay-like, a tablet was produced in the same manner as in Example.

<Measurement of characteristics of silicone resin tablet>
(Type A durometer hardness)
With respect to the tablets of Examples 1 to 8 and Comparative Example 3 which were allowed to stand at 25 ° C. for 3 minutes, the needle of a type A durometer was pressed against the tablet according to JIS: K6253, and the value after 1 minute was measured.

(Automatic transportability)
The tablets were filled in a tablet magazine provided in a TOWA multi-plunger transfer molding machine, and an automatic conveyance test was performed. Those which could be conveyed without any problem were judged as "possible" for automatic conveyance, and those for which a tablet could not be produced or those which could not be conveyed because the tablet was deformed during conveyance were judged as "impossible" for automatic conveyance.

(Measurement of light reflectance)
After transfer molding the silicone resin tablets obtained in Examples 1 to 8 under the conditions of a mold temperature of 180 ° C., a pressure of 14 MPa and a curing time of 300 seconds, post-curing was performed at 150 ° C. for 2 hours to obtain a thickness of 3. A test piece of 0 mm was prepared. Using the obtained test piece, the light reflectance at a wavelength of 460 nm was measured using an integrating sphere spectrophotometer CM600d (manufactured by Konica Minolta, Inc.).

  In addition, the unit of the compounding amount of each raw material shown in each table is all parts by mass, and the portion described with "-" means that there is no compounding of the corresponding raw material.

Details of * 1 to 11 in Tables 1 and 2 are as follows.
* 1: Thermosetting silicone resin (Synthesis example 1, liquid at 25 ° C)
* 2: Thermosetting silicone resin (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., product name: SILRES H 62C, liquid at 25 ° C.)
* 3: Thermosetting silicone resin (Synthesis example 2, liquid at 25 ° C)
* 4: Silicone resin A (Synthesis example 3)
* 5: Silicone resin B (Synthesis example 4)
* 6: Silicone resin C (Synthesis example 5)
* 7: Platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex (manufactured by Wako Pure Chemical Industries, Ltd., platinum 1.7% by mass)
* 8: Fused silica (manufactured by Denki Kagaku Kogyo Kyokai, product name: FB-950, central particle size 26 μm)
* 9: Fused silica (manufactured by Admatechs Co., Ltd., product name: SO-25R, central particle size 1 μm)
* 10: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., product name: CR63, center particle size 0.2 μm)
* 11: Carbon black (Mitsubishi Chemical Corporation, product name: MA-100, central particle size 23 nm)

  As shown in Table 1, according to the silicone resin tablets of Examples 1 to 8, the automatic transportability during transfer molding was good, and a cured product (molded product) having excellent optical properties was obtained by transfer molding. Was confirmed.

  REFERENCE SIGNS LIST 100 optical semiconductor element 101 transparent sealing resin 102 bonding wire 103 reflector insulating resin molded body 104 Ni / Ag plating 105 metal wiring 106 phosphor 107 Solder bump, 110: Optical semiconductor element mounting substrate, 150: Resin injection port, 151: Mold, 200: Optical semiconductor element mounting area, 300: LED element, 301: Bonding wire, 302: Transparent sealing resin, 303 ... Reflector, 304 lead, 305 phosphor, 306 die bonding material, 400 copper-clad laminate, 401 base material, 402 resin layer, 403 copper foil, 404 sealing resin, 408 adhesive layer, 409 ... bonding wire, 410 ... optical semiconductor element, 500, 600 ... optical semiconductor device, 601 ... base material, 602 ... conductor member, 603 ... tree Layers, 604 ... sealing resin, 608 ... adhesive layer, 609 ... bonding wire, 610 ... optical semiconductor element.

Claims (8)

Including silicone resin and pigment,
A silicone resin tablet for a reflector of an optical semiconductor device, wherein the silicone resin contains a silicone resin in a solid state at 25 ° C. and a thermosetting silicone resin in a liquid state at 25 ° C.,
The silicone resin in a solid state at 25 ° C., wherein the proportion of an aryl group or a cycloalkyl group bonded to a silicon atom is 20 mol% or more based on the total amount of the hydrocarbon groups bonded to the silicon atom. Resin
A silicone resin tablet, wherein the thermosetting silicone resin liquid at 25 ° C. has an alkenyl group and a SiH group.   The silicone resin tablet according to claim 1, wherein the pigment contains at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, antimony oxide, zirconium oxide, and inorganic hollow particles. .   A cured product formed using the silicone resin tablet according to claim 1.   A substrate for mounting an optical semiconductor element, comprising a molded body formed from the silicone resin tablet according to claim 1. It has a concave portion composed of a bottom surface and a wall surface, and the bottom surface of the concave portion is a mounting portion of the optical semiconductor element,
An optical semiconductor element mounting substrate, wherein at least a part of the wall surface of the concave portion is formed of a molded body formed from the silicone resin tablet according to claim 1. A substrate, comprising a first connection terminal and a second connection terminal provided on the substrate,
3. An optical semiconductor element mounting substrate, comprising a molded body formed from the silicone resin tablet according to claim 1 between the first connection terminal and the second connection terminal.   An optical semiconductor device, comprising: the optical semiconductor element mounting substrate according to claim 4; and an optical semiconductor element mounted on the optical semiconductor element mounting substrate.   A method for manufacturing an optical semiconductor element mounting substrate having a concave portion composed of a bottom surface and a wall surface, wherein at least a part of the wall surface of the concave portion is transfer-molded using the silicone resin tablet according to claim 1 or 2. A method for manufacturing a substrate for mounting an optical semiconductor element, the method comprising:

Images