JP6566121B2 - Thermosetting resin composition, substrate for mounting optical semiconductor element, method for manufacturing the same, and optical semiconductor device - Google Patents

Description

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

  Thermosetting resins are used in a wide range of applications because they exhibit various excellent properties derived from their unique cross-linked structures. As one of the applications, in recent years, an optical semiconductor device in which an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor are combined is used for an outdoor display, a mobile phone, and the like because of advantages such as high energy efficiency and long life. It is applied to various applications such as liquid crystal backlights and in-vehicle applications, and its demand is expanding.

  One type of optical semiconductor device is a surface-mounted optical semiconductor device. Some surface-mount optical semiconductor devices have an optical semiconductor element and a reflector (reflecting portion) provided so as to surround the optical semiconductor element. Patent Document 1 discloses a resin composition for a mounting package for housing an optical semiconductor element using a silicone resin having a structure in which any one of a vinyl group and an allyl group and a hydrogen atom is directly bonded to a silicon atom. Has been.

  Here, in the operation | work which heat-hardens a thermosetting resin composition and produces a molded object, each process may be performed continuously. For example, Patent Literature 2 describes a resin sealing device for sealing and molding an electronic component mounted on a lead frame at the time of transfer molding with a resin material. A method for sealing is disclosed.

JP 2009-21394 A JP 2014-222711 A

  However, in the case of a cured product formed from a thermosetting resin composition containing a silicone resin, there is a possibility that cracks or cracks may occur in the molded product during the process when molding is performed continuously.

  The present invention has been made in view of the above circumstances, and is a thermosetting resin composition capable of forming a tough molded body in which cracks and cracks are unlikely to occur, and light using the thermosetting resin composition It is an object of the present invention to provide a semiconductor element mounting substrate, a method for manufacturing the same, and an optical semiconductor device.

  The present invention relates to a thermosetting resin composition containing a silicone resin and a pigment containing a hydrosilyl group-containing silicone resin and an alkenyl group-containing silicone resin having an alkenyl group equivalent of 50 to 1000 g / mol.

  The alkenyl group-containing silicone resin may have 75 mol% or more of alkenyl groups based on the total amount of organic groups bonded to silicon atoms. The alkenyl group-containing silicone resin may have a weight average molecular weight of 200 to 10,000.

［式中、Ｒ^１１はそれぞれ独立にアルケニル基を示す。］Furthermore, the alkenyl group-containing silicone resin may have a structure represented by the following formula (I).

[Wherein, each R ¹¹ independently represents an alkenyl group. ]

  The thermosetting resin composition of the present invention may contain 0.0005 to 35% by mass of the alkenyl group-containing silicone resin based on the total amount of the thermosetting resin composition.

  In the thermosetting resin composition, from the viewpoint of improving the light reflectance of the cured product, the pigment is at least one selected from the group consisting of titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide, and zirconium oxide. The white pigment may be included, and hollow particles may be included.

  The present invention also relates to a cured product formed from the thermosetting resin composition. In another aspect, the present invention relates to an optical semiconductor element mounting substrate having a molded body formed from the thermosetting resin composition described above. The optical semiconductor element mounting substrate has a recess composed of a bottom surface and a wall surface, the bottom surface of the recess is a mounting portion for the optical semiconductor element, and at least a part of the wall surface of the recess is the thermosetting resin composition described above. It is the molded object formed from the thing. The optical semiconductor element mounting substrate of the present invention includes a substrate, a first connection terminal and a second connection terminal provided on the substrate, and the first connection terminal and the second connection terminal are provided. In between, you may have the molded object formed from the above-mentioned thermosetting resin composition.

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

  The present invention also relates to a method for manufacturing a substrate for mounting an optical semiconductor element having a recess composed of 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 recess by transfer molding or compression molding using the thermosetting resin composition described above.

  INDUSTRIAL APPLICABILITY According to the present invention, a thermosetting resin composition capable of forming a tough cured product that is less likely to crack and crack, a substrate for mounting an optical semiconductor element using the thermosetting resin composition, and a method for manufacturing the same. In addition, an optical semiconductor device can be provided.

It is a perspective view which shows one Embodiment of the board | substrate for optical semiconductor element mounting. It is the schematic which shows one Embodiment of the process of manufacturing the board | substrate for optical semiconductor element mounting. It is a perspective view which shows one Embodiment in the state which mounted the optical semiconductor element in the board | substrate for optical semiconductor element mounting. It is a schematic cross section showing one embodiment of an optical semiconductor device. It is a schematic cross section which shows other embodiment of an optical semiconductor device. It is a schematic cross section which shows other embodiment of an optical semiconductor device. It is a schematic cross section which shows one Embodiment of a copper clad laminated board. It is a schematic cross section which shows an example of the optical semiconductor device produced using the copper clad laminated board. It is a schematic cross section which shows other embodiment 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.

  Note that in this specification, the use of numerical ranges by endpoints includes all numbers included in the range (for example, 0.5 to 5, 0.5, 1.5, 2, 2.75, 3 3.80, 4, 5, etc.) and any range within that range.

[Thermosetting resin composition]
The thermosetting resin composition of this embodiment contains a silicone resin and a pigment containing a hydrosilyl group-containing silicone resin and an alkenyl group-containing silicone resin having an alkenyl group equivalent of 50 to 1000 g / mol. Hereinafter, each component contained in the thermosetting resin composition of this embodiment is demonstrated.

(Hydrosilyl group-containing silicone resin)
The hydrosilyl group-containing silicone resin is not particularly limited as long as it is a silicone resin having a hydrosilyl group that is a group (Si-H) in which a hydrogen atom is directly bonded to a silicon atom.

The hydrosilyl group-containing silicone resin may have, for example, a unit represented by HSiO _3/2 , a unit represented by HSiO _2/2 , or a unit represented by HSiO _1/2 as a structural unit having a hydrosilyl group. it can.

  The structural unit having a hydrosilyl group is, for example, methylmethoxydisilane, dimethoxydisilane, methoxytrisilane, ethylmethoxydisilane, dimethylethoxysilane, propyldiethoxysilane, propylethoxydisilane, n-butyldimethoxysilane, phenyldimethoxysilane, phenylmethoxy. Alkoxyhydroxysilanes such as disilane and triethoxysilane; methyldichlorosilane, n-propyldichlorosilane, isopropyldichlorosilane (1,1-dichloro-2-methyl-1-silapropane), n-butyldichlorosilane, n-pentyldi It can introduce | transduce into a silicone resin using alkyl dichlorosilanes, such as chlorosilane, cyclopentyl dichlorosilane, and cyclohexyl dichlorosilane.

  The hydrosilyl group-containing silicone resin may have a structure in which a group other than a hydrogen atom is bonded to a silicon atom, that is, a structural unit other than a hydrosilyl group. Examples of the structural unit other than the hydrosilyl group include a structural unit in which an organic group having 1 to 12 carbon atoms is bonded to a silicon atom. From the viewpoint of ease of synthesis, an organic group having 1 to 8 carbon atoms is silicon. It may be a structural unit bonded to an atom. The organic group is preferably a hydrocarbon group from the viewpoint of ease of synthesis, 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 hydrogen atoms are partially substituted with chlorine atoms, fluorine atoms, or the like. From the viewpoint of further improving the ease of synthesis and hardness of the silicone resin, the organic group is preferably an aryl group, and more preferably a phenyl group.

The hydrosilyl group-containing silicone resin may have a unit represented by R ¹ SiO _3/2 as a structural unit other than the hydrosilyl group, and a unit represented by R ¹ SiO _3/2 and R ² SiO It may have at least one unit selected from a unit represented by _2/2 , a unit represented by R ³ SiO _1/2 and a unit represented by SiO _4/2 .

R ¹ , R ² and R ³ each independently represent a monovalent organic group, and are preferably a C 1-12 hydrocarbon group from the viewpoint of availability. As a hydrocarbon group, the same thing as the hydrocarbon group mentioned above is illustrated. From the viewpoint of ease of synthesis of the hydrosilyl group-containing silicone resin, R ¹ , R ² and R ³ are preferably each independently an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.

  The weight average molecular weight of the hydrosilyl group-containing silicone resin is not particularly limited, but from the viewpoint of improving the moldability of the thermosetting resin composition, it is preferably 200 or more, more preferably 1000 or more, and 2000 or more. Further preferred. On the other hand, the weight average molecular weight of the hydrosilyl group-containing silicone resin is preferably 15000 or less, more preferably 10,000 or less, and further preferably 7000 or less, from the viewpoint of further improving the hardness of the cured product. That is, the weight average molecular weight of the hydrosilyl group-containing silicone resin may be 200 to 15000, 1000 to 10,000, or 2000 to 7000.

The weight average molecular weight Mw in the present specification can be obtained by measuring under the following conditions using a standard polystyrene calibration curve by gel permeation chromatography (GPC).
(GPC conditions)
Pump: L-6200 type (manufactured by Hitachi, Ltd., trade name)
Column: TSKgel-G5000HXL and TSKgel-G2000HXL (trade name, manufactured by Tosoh Corporation)
Detector: L-3300RI type (manufactured by Hitachi, Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 30 ° C
Flow rate: 1.0 mL / min

  Although content of the hydrosilyl group containing silicone resin in a thermosetting resin composition is not specifically limited, From a viewpoint of improving the moldability of a thermosetting resin composition, 0.01-40 mass with respect to the whole resin composition. %, More preferably 0.1 to 35% by mass, and still more preferably 1.0 to 30% by mass.

(Alkenyl group-containing silicone resin)
The thermosetting resin composition of the present embodiment contains an alkenyl group-containing silicone resin having an alkenyl group equivalent of 50 to 1000 g / mol. The alkenyl group equivalent represents the weight of the alkenyl group-containing silicone resin necessary to obtain 1 mol of alkenyl group. The alkenyl group can form a cured product of the thermosetting resin composition by an addition reaction with the hydrosilyl group contained in the above-described hydrosilyl group-containing silicone resin, preferably in the presence of a curing catalyst. When the alkenyl group equivalent is within the above range, the resin structure after curing has a high crosslink density.

  When the optical semiconductor device is continuously formed using an apparatus such as Patent Document 2, a cause of cracking or cracking in the molded body is that the hardness of the molded body is low. That is, since it is difficult to control the transport of the molded body by a machine, the molded body cannot withstand the impact generated during transport. In particular, when the molded body is a reflector of an optical semiconductor device, since it has a complicated shape, pressure tends to concentrate on a part thereof, and the possibility that a crack or a crack will occur increases. In the present embodiment, since the above alkenyl group-containing silicone resin is used, the number of portions capable of hydrosilylation reaction increases, and the formed cured product has a high crosslinking density. Therefore, it becomes possible to obtain a molded body having high hardness. A molded body having high hardness can reduce the occurrence of cracks or cracks and improve the productivity of the optical semiconductor device.

In order to further improve the crosslinking density and hardness of the cured product, the alkenyl group equivalent of the alkenyl group-containing silicone resin is preferably 50 to 500 g / mol, more preferably 50 to 300 g / mol, and 50 to More preferably, it is 250 g / mol. The alkenyl group equivalent of the silicone resin can be calculated according to the following formula by measuring the iodine value.
Y = M _I2 × 100 / X

In the formula, X represents an iodine value, Y represents an alkenyl group equivalent, and M _I2 represents a molecular weight of an iodine molecule. The iodine value can be calculated by adding iodine to an unsaturated bond and titrating excess iodine with a sodium thiosulfate solution according to the method described in JIS K 0070: 1992.

  The alkenyl group present in the silicone resin is not necessarily bonded directly to the silicon atom. As an alkenyl group, a vinyl group, an allyl group, 1-butenyl group, 2-butenyl group, and 2-pentenyl group are mentioned, for example. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance and light resistance.

  The alkenyl group can be introduced into the silicone resin using, for example, a silane compound having an alkenyl group. Examples of the silane compound having an alkenyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, methylvinyldimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and methylallyldimethoxysilane. And alkenylalkoxysilane.

  The alkenyl group-containing silicone resin preferably has a ladder structure as a siloxane skeleton. The ladder structure refers to a structure in which adjacent structural units are connected via two or more atoms. By using a silicone resin having a ladder structure, the crosslink density after curing of the thermosetting resin composition is further increased, and a tough cured product is more easily formed.

Examples of the silicone resin having a ladder structure include compounds having a structural unit as shown in the following formula (I). In the formula, each R ¹¹ independently represents an alkenyl group. In addition, it is understood that the following formula (I) has the above structural unit and two oxygen atoms that connect the structural unit, and the silicone resin having a ladder structure is represented by (R ¹¹ SiO _3/2 ) _2. It may have a structure.

The silicone resin having a ladder structure preferably has a structure represented by the formula (I) continuously. In that case, the silicone resin can have a structure represented by the following formula (I ′), for example. In the following formula (I ′), three sets of structural units, two sets of two oxygen atoms connecting them, and two oxygen atoms connecting constituent units (not shown) adjacent to the right are 1 It is understood that you have a pair.

  When the silicone resin continuously has the structure represented by the formula (I), the number of repeating units of the structure represented by the formula (I) is not particularly limited, but is 3 to 5000 from the viewpoint of further improving the crosslinking density after curing. It is preferable that it is 5 to 3000, more preferably 10 to 2000.

The alkenyl group-containing silicone resin may have a group other than the alkenyl group. Examples of the structural unit having a group other than an alkenyl group include a structural unit represented by R ⁴ SiO _3/2 or R ⁵ SiO _2/2 . That is, the alkenyl group-containing silicone resin has a structure represented by the formula (I) ((R ¹¹ SiO _3/2 ) ₂ ) and a structure represented by R ⁴ SiO _3/2 or R ⁵ SiO _2/2. You may do it. R ⁴ and R ⁵ each independently represent a monovalent organic group, and are preferably a hydrocarbon group having 1 to 12 carbon atoms from the viewpoint of availability. As a hydrocarbon group, the same thing as above-mentioned R < ¹ >, R < ² > and R < ³ > is illustrated.

The alkenyl group-containing silicone resin preferably has 75% by mole or more of alkenyl groups, more preferably 85% by mole or more, and more preferably 95% by mole or more based on the total amount of organic groups directly bonded to silicon. preferable. By including such an alkenyl group-containing silicone resin, the crosslink density of the cured resin is further increased, the cured product of the thermosetting resin composition is hard and difficult to break, and is further improved by automatic transportability during continuous molding. It will be excellent. From the viewpoint of increasing the crosslinking density, the upper limit of the amount of alkenyl groups present in the alkenyl group-containing silicone resin is preferably as large as possible, and may be 100 mol%. The amount of alkenyl group can be calculated by measuring ¹ H-NMR of the silicone resin.

The alkenyl group-containing silicone resin preferably has at least 22 mol%, more preferably at least 23 mol%, and even more preferably at least 24 mol%, based on the total amount of elements directly bonded to silicon. . By including such an alkenyl group-containing silicone resin, the cured product of the thermosetting resin composition is hard and difficult to break, and is more excellent in automatic transportability during continuous molding. The upper limit of the amount of alkenyl groups present in the alkenyl group-containing silicone resin is not particularly limited, but may be 30 mol%. The amount of alkenyl group can be calculated by measuring ¹ H-NMR of the silicone resin.

  The weight average molecular weight of the alkenyl group-containing silicone resin is not particularly limited, but is preferably 200 or more, more preferably 800 or more, and 1200 or more from the viewpoint of improving the moldability of the thermosetting resin composition. Further preferred. From the viewpoint of further improving the hardness of the cured product, the weight average molecular weight of the alkenyl group-containing silicone resin is preferably 10,000 or less, more preferably 8000 or less, and even more preferably 7000 or less. That is, the weight average molecular weight of the alkenyl group-containing silicone resin may be 200 to 10,000, 800 to 8000, or 1200 to 7000.

  The content of the alkenyl group-containing silicone resin according to this embodiment in the thermosetting resin composition is not particularly limited. The alkenyl group-containing silicone resin according to this embodiment is, for example, preferably 0.001 to 70 parts by mass, more preferably 0.01 to 65 parts by mass with respect to 100 parts by mass of the total amount of the silicone resin. More preferably, it is 0.1-60 mass parts. The alkenyl group-containing silicone resin according to this embodiment is preferably 0.0005 to 35% by mass, more preferably 0.008 to 30% by mass, based on the total amount of the resin composition. More preferably, it is 01-20 mass%. Within this range, the thermosetting resin composition is more excellent in moldability.

  The alkenyl group-containing silicone resin may be used after diluted in an organic solvent in order to further improve the handleability. Examples of the organic solvent include, but are not limited to, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran Ether solvents such as toluene; aromatic solvents such as toluene, xylene and mesitylene. From the viewpoint of solubility of the alkenyl group-containing silicone resin, the organic solvent may be an alcohol solvent, a ketone solvent, or a nitrogen atom-containing solvent.

  The mixing ratio of the alkenyl group-containing silicone resin and the hydrosilyl group-containing silicone resin in the silicone resin is not particularly limited, but from the viewpoint of further enhancing the strength and heat resistance, the number of SiH groups (Y) in the hydrosilyl group-containing silicone resin The ratio (Y / X, molar ratio) to the number (X) of alkenyl groups in the alkenyl group-containing silicone resin component is preferably 0.3 ≦ Y / X ≦ 3, and 0.5 ≦ Y / X More preferably, ≦ 2, more preferably 0.7 ≦ Y / X ≦ 1.5.

  The silicone resin according to the present embodiment can contain other silicone resins in addition to the hydrosilyl group-containing silicone resin and alkenyl group-containing silicone resin described above as long as the effects of the present invention are not impaired.

(Curing catalyst)
From the viewpoint of reactivity, the resin composition of the present embodiment preferably contains a curing catalyst that promotes the hydrosilylation reaction of the silicone resin. Examples of the curing catalyst include a calsted catalyst; platinum alone; a carrier (alumina, silica, carbon black, etc.) supported with solid platinum; chloroplatinic acid; a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc. 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.

Platinum - The olefin complexes, for _{example, Pt (CH 2 = CH 2} ) 2 (PPh 3) 2 and _{Pt (CH 2 = CH 2)} 2 Cl 2 and the like. Examples of the platinum-vinylsiloxane complex include platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex and platinum-1,3-divinyltetramethyldisiloxane complex. Is mentioned. Examples of the platinum-phosphine complex include platinum- (PPh ₃ ) ₄ and platinum- (PBu ₃ ) ₄ . Examples of the platinum-phosphite complex include platinum- [P (OPh) ₃ ] ₄ and platinum- [P (OBu) ₃ ] ₄ . In the formula, Bu represents a butyl group, and Ph represents a phenyl group.

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

  The amount of the curing catalyst contained in the thermosetting resin composition is not particularly limited, but from the viewpoint of further improving the curability of the thermosetting resin composition, 0.005 with respect to 100 parts by mass of the total amount of the silicone resin. -0.5 mass part is preferable, 0.01-0.3 mass part is more preferable, 0.01-0.2 mass part is still more preferable. The amount of the curing catalyst relative to the entire resin composition is preferably 0.01 to 3 ppm, more preferably 0.05 to 2.5 ppm in terms of metal weight, from the viewpoint of further improving curability. More preferably, the content is 0.08 to 2.2 ppm.

(Pigment)
A pigment adds the color according to a use to the hardened | cured material of the thermosetting resin composition concerning this embodiment. The pigment which concerns on this embodiment can be selected according to the intended purpose of the hardened | cured material of the thermosetting resin composition produced. Examples of the pigment include a white pigment, a black pigment, a red pigment, a yellow pigment, an orange pigment, a purple (dark blue) 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. Examples of red pigments include red lead, iron oxide red, quinacridone, diketopyrrolopyrrole, anthraquinone, perylene, perinone, and indigoid. Examples of yellow pigments include chrome lead and zinc yellow. Examples of blue pigments include ultramarine blue, prussian blue (potassium ferrocyanide), phthalocyanine blue, anthraquinone, and indigoid. Examples of the orange pigment include diketopyrrolopyrrole, perylene, anthraquinone, perinone, quinacridone, and indigoid. Examples of purple (dark blue) color 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.

  When light reflection characteristics are required for the thermosetting resin composition, it is preferable to use a white pigment as the pigment. When the thermosetting resin composition contains a white pigment, the cured product of the thermosetting resin composition has an excellent reflectance, and when used as a light reflecting material provided in a substrate for mounting an optical semiconductor element In addition, a high-brightness optical semiconductor device can be obtained.

  Examples of the white pigment include titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide, and zirconium oxide. From the viewpoint of obtaining better light reflectivity, titanium oxide, alumina, and zinc oxide are preferable. These may be used alone or in combination of two or more.

  Hollow particles may be used as the white pigment. The hollow particle is a particle having a void inside, and the substance constituting the outer shell is not particularly limited. Hollow particles are useful as white pigments because they refract and reflect incident light at the surface and inner wall. Examples of the hollow particles include inorganic hollow particles and organic hollow particles. As the inorganic hollow particles, metal oxides such as inorganic glass and silica; metal salts such as calcium carbonate, barium carbonate, calcium silicate, and nickel carbonate can be preferably used. Specifically, for example, sodium silicate glass , Aluminum silicate glass, borosilicate soda glass, shirasu particles and the like. As the organic hollow particles, polystyrene resins, poly (meth) acrylate resins, and cross-linked products thereof can be suitably used. From the viewpoint of heat resistance and pressure strength, the outer shell of the hollow particles is at least one selected from the group consisting of sodium silicate glass, aluminum silicate glass, borosilicate soda glass, shirasu, crosslinked styrene resin, and crosslinked acrylic resin. It is preferable that it is comprised from the material of these.

When the white pigment is used, the particle size of the white pigment is not particularly limited, but is preferably in the range of 0.05 to 50 μm, more preferably in the range of 0.08 to 30 μm, and 0.1 to 10 μm. More preferably, it is in the range. When the center particle diameter of the white pigment is 0.1 μm or more, the dispersibility becomes better, and when it is 50 μm or less, the light reflection property of the cured product becomes better. The central particle diameter can be determined as a mass average value D ₅₀ (or median diameter) in particle size distribution measurement by a laser light diffraction method.

  The pigment content in the thermosetting resin composition is preferably in the range of 1 to 90% by mass, more preferably in the range of 5 to 90% by mass, based on the total amount of the resin composition, and 10 to 80%. More preferably, it is mass%. When the white pigment is used, if the content is 1% by mass or more, the light reflection property of the cured product is further improved, and if it is 90% by mass or less, the moldability of the thermosetting resin composition is further improved. From the same viewpoint, the pigment content is preferably 50 to 2000 parts by mass, more preferably 80 to 1700 parts by mass, and more preferably 100 to 1500 parts by mass with respect to 100 parts by mass of the total amount of the silicone resin. More preferably, it is part.

(Other ingredients)
In addition to the components described above, the thermosetting resin composition includes inorganic fillers, coupling agents, curing retarders, thermosetting resins other than silicone resins, antioxidants, mold release agents, dispersants, ion scavengers, and the like. These various additives can be further contained.

  From the viewpoint of reducing the linear expansion coefficient, the thermosetting resin composition preferably contains an inorganic filler. Examples of the inorganic filler include silica, antimony oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate.

  In addition, in this specification, it shall belong to a pigment in principle about the substance which has the effect of both a pigment and an inorganic filler. However, when the thermosetting resin composition contains two or more kinds of substances having the effects of both the pigment and the inorganic filler, one of the substances belongs to the inorganic filler. Substances other than titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide and zirconium oxide are given priority as substances belonging to the inorganic filler.

  The center particle diameter of the inorganic filler is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.4 to 80 μm, from the viewpoint of improving the packing efficiency with the pigment. More preferably, it is 5-75 micrometers. The content of the inorganic filler in the thermosetting resin composition is in the range of 4 to 85% by mass on the basis of the total amount of components that become a solid content after curing of the thermosetting resin composition from the viewpoint of further improving moldability. It is preferable that it is 10-80 mass%, and it is still more preferable that it is 20-80 mass%.

  From the viewpoint of further improving the strength and hardness of the cured product, the total amount of the inorganic filler and the pigment contained in the thermosetting resin composition is preferably 6 to 98% by mass based on the total amount of the resin composition, It is more preferably 15 to 95% by mass, and further preferably 30 to 90% by mass.

  A coupling agent may be added to the thermosetting resin composition as necessary. By including a coupling agent, 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 silane coupling agents and titanate coupling agents. As the silane coupling agent, generally known compounds such as epoxy silane, amino silane, cationic silane, vinyl silane, acrylic silane, and mercapto silane can be used. The coupling agent may be a composite system of the silane coupling agent. It is preferable that the usage-amount of a coupling agent shall be 0.01-5 mass% on the basis of the thermosetting resin composition whole quantity from a viewpoint of improving sclerosis | hardenability. A pigment or an inorganic filler may be previously treated with the above coupling agent.

  A curing retarder may be added to the thermosetting resin composition from the viewpoints of improving storage stability and adjusting reactivity. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. 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 tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retardants, those having good retarding activity and colorless or pale yellow such as pale yellow are preferable. A hardening retarder may be used independently or may use 2 or more types together.

  The addition amount of the curing retardant is preferably in the range of 0.1 to 100 mol and more preferably in the range of 1 to 50 mol with respect to 1 mol of the curing catalyst used.

  For the purpose of modifying the characteristics, it is possible to add a thermosetting resin other than the silicone resin to the thermosetting resin composition as long as the characteristics are not adversely affected. 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, an epoxy resin is preferable from the viewpoint of excellent adhesion to metal parts. As the thermosetting resin, those which are colorless or relatively uncolored such as pale yellow are preferable.

  The epoxy resin is not particularly limited. 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, vinyl cyclohexylene dioxide, 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. From the viewpoints of heat resistance and ultraviolet resistance, alicyclic epoxy resins are preferable, and triglycidyl isocyanurate is more preferable from the same viewpoint.

  When using an epoxy resin, it is preferable to further contain a curing agent for the epoxy resin. From the viewpoint of heat discoloration, the curing agent is preferably an acid anhydride curing agent. Examples of the acid anhydride curing agent include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methyl hydride. Examples thereof include nadic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, and anhydrides of aliphatic acids (cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, etc.). These epoxy resins or curing agents may be used alone or in combination of two or more.

(Characteristics of thermosetting resin composition)
When using the thermosetting resin composition of this embodiment as a light reflection material, it is preferable that the light reflectivity after hardening will be 80% or more at any wavelength of 440 to 700 nm. If the light reflectance is 80% or more, the luminance of the optical semiconductor device can be further improved. Further, from the viewpoint of being suitable for an optical semiconductor device using a blue light emitting diode, the light reflectivity at a wavelength of 460 nm after curing is preferably 80% or more, and more preferably 90% or more.

  When a thermosetting resin composition is used as a light reflecting material, from the viewpoint of improving heat resistant colorability, the light reflectance of the cured product is a wavelength of 440 to 700 nm after a heat resistance test that is exposed to an environment of 150 ° C. for 1000 hours. In any of the cases, it is preferably 80% or more. Further, from the viewpoint of being suitable for an optical semiconductor device using a blue light emitting diode, the light reflectance at a wavelength of 460 nm is more preferably 85% or more and 90% or more at the time of measurement after the heat resistance test described above. More preferably. The light reflection characteristics of such a thermosetting resin composition can be realized by appropriately adjusting the blending amounts of various components constituting the resin composition, and more specifically, for example, colorless heat This can be achieved by highly filling the cured resin component and the white pigment having a high refractive index. In the present specification, the light reflectance is a value measured using an integrating sphere spectrophotometer after preparing a cured product having a thickness of 3 mm.

  In the thermosetting resin composition of the present embodiment, the type D durometer hardness after curing is preferably 40 or more, more preferably 50 or more, and further preferably 55 or more. If hardness is 40 or more, the toughness of a molded object will become more favorable. The upper limit of hardness is not particularly limited, but can be about 100. The type D durometer hardness can be measured according to the method described in JIS K 6253-3: 2012, and is molded with a thickness of 3 mm after transfer molding under conditions of a temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds. It is a measure of the hardness of the body.

  From the viewpoint of reducing cracks or cracks, the thermosetting resin composition of the present embodiment preferably has a breaking strength after curing of 15 or more, more preferably 20 or more, and preferably 25 or more. Further preferred. The breaking strength was measured when a three-point bending fracture test was performed at room temperature on a test piece having a thickness of 4 mm after transfer molding in accordance with JIS K 7171: 2008 under conditions of a temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds. Value.

[Method for producing thermosetting resin composition]
Although the manufacturing method of the thermosetting resin composition which concerns on this embodiment is not specifically limited, For example, you may provide the following kneading | mixing processes and a grinding | pulverization process.

(Kneading process)
The thermosetting resin composition can be prepared by uniformly dispersing and mixing the various components exemplified above, and the mixing means, mixing conditions and the like are not particularly limited. Examples of the preparation method include a method of kneading various components using an apparatus such as a mixing roll, an extruder, a kneader, a roll, an extruder, a raking machine, a stirring mixer that combines rotation and revolution, and the like. The kneading type is not particularly limited, but melt kneading is preferable from the viewpoint of easy work, and kneading is preferably performed at 15 to 30 ° C. from the viewpoint of simplification of the process. When heating is required, the temperature range may be, for example, 30 to 100 ° C. When the melt kneading temperature is 30 ° C. or higher, various components can be melted and kneaded more sufficiently, and the dispersibility tends to be further improved. On the other hand, when the melt-kneading is performed at 100 ° C. or lower, the high molecular weight of the resin composition can be further suppressed, and the resin composition can be further suppressed from being cured before molding a molded product such as a substrate. The kneading time may be 5 to 40 minutes or 10 to 30 minutes. When the melt-kneading time is 5 minutes or longer, the resin can be prevented from seeping out from the mold during molding of the substrate and the like, and when it is within 40 minutes, the polymer composition of the resin composition can be easily controlled and molded. It can suppress more that a resin composition hardens before.

  In the kneading step, first, premixing may be performed in which the hydrosilyl group-containing silicone resin and the alkenyl group-containing silicone resin are mixed in advance, and then the other components may be added to perform the above mixing. The thermosetting resin composition obtained by premixing has improved storage stability and is more excellent in moldability during molding. The hydrosilyl group-containing silicone resin and alkenyl group-containing silicone resin used in the premixing may be a part of the thermosetting resin composition, or may be the total amount.

  The thermosetting resin composition that has been subjected to the kneading step is preferably in a state that allows the dry pulverization described later. Therefore, you may perform the process of cooling a thermosetting resin composition as needed.

(Crushing process)
In the pulverization step, for example, the thermosetting resin composition is dry pulverized. The dry pulverization can be performed using a pulverizer such as a high-speed stirring mill, a Henschel mixer, a power mill, a jet mill, or a roll granulator. These pulverizers can be properly used depending on the target powder particle size.

  The thermosetting resin composition according to this embodiment is preferably processed into a tablet shape. The tablet shape in the present specification means a solid shape that maintains a constant shape, for example, substantially does not change in shape over time when left for about 30 minutes. By being processed into a tablet shape, the handleability is further improved, and the efficiency of transfer molding, compression molding and the like using the thermosetting resin composition can be increased. 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 a cylindrical shape is preferable from the viewpoint of handleability.

  The tablet molding conditions are not particularly limited. For example, the tablet-like thermosetting resin composition can be obtained by pressure molding at room temperature under conditions of 0.5 to 60 MPa for about 1 to 15 seconds. The pressure molding for tablet molding is a process that is clearly different from transfer molding or compression molding described later.

  The tablet-like thermosetting resin composition according to this embodiment preferably has a type A durometer hardness of 50 or more, more preferably 55 or more, and still more preferably 60 or more. If the hardness is 50 or more, the tablet is not easily deformed, and the handling property is improved. Since the hardness of the tablet-like thermosetting resin composition is as good as possible, the upper limit value of the type A durometer hardness is not particularly limited, but can be about 100. The type A durometer hardness is preferably a value measured after the tablet-like thermosetting resin composition is allowed to stand at 25 ° C. for 3 minutes.

  The type A durometer hardness can be measured according to the method described in JIS K 6253-3: 2012. In the present specification, a value obtained by pressing a type A durometer needle against the tablet-like thermosetting resin composition and reading a value after 1 minute is defined as type A durometer hardness.

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

  About the method of coat | covering a filler to a to-be-adhered body, if it can contact with a tablet-like thermosetting resin composition, there will be no restriction | limiting in particular. For example, a method in which a filler is put in a container or a bag, and a tablet-like thermosetting resin composition is coated by vibration using a machine and a method in which the filler is manually sprinkled may be mentioned.

  The thermosetting resin composition of this embodiment is used in various applications such as electrical insulating materials, optical semiconductor sealing materials, adhesive materials, paint materials, and epoxy resin molding materials for transfer molding or compression molding that require high heat resistance. Useful. In particular, the thermosetting resin composition of the present embodiment is useful as a material for transfer molding. In addition, when using the thermosetting resin composition of this embodiment for a light reflection use, it is preferable that it is white.

[Cured product]
The hardened | cured material of this embodiment can be formed by thermosetting the above-mentioned thermosetting resin composition. The conditions for thermosetting are not particularly limited, but can be cured by heating at a temperature of 170 to 200 ° C. for 60 to 300 seconds, for example. You may perform thermosetting as a part of process included in the below-mentioned shaping | molding method.

[Optical semiconductor device mounting substrate]
The substrate for mounting an optical semiconductor element according to the present embodiment has a recess composed of a bottom surface and a wall surface. A molded body in which the bottom surface of the recess is an optical semiconductor element mounting portion (optical semiconductor element mounting region), and at least a part of the wall surface of the recess, that is, the inner peripheral side surface of the recess, is formed from the thermosetting resin composition of the present embodiment. It consists of

  FIG. 1 is a perspective view showing an embodiment of a substrate for mounting an optical semiconductor element. 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 terminal). Insulating resin molded body 103 ′ provided between the terminals) and the reflector 103, and formed of the metal wiring 105 formed with the Ni / Ag plating 104 and the insulating resin molded body 103 ′ and the reflector 103. An optical semiconductor element mounting region (concave portion) 200 is provided. The bottom surface of the recess 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 recess 200 is composed of the reflector 103. The reflector 103 and the insulating resin molded body 103 ′ are molded bodies formed using the thermosetting resin composition of the present embodiment.

  Although the manufacturing method of the board | substrate for optical semiconductor element mounting is not specifically limited, For example, it can manufacture by transfer molding or compression molding using a thermosetting resin composition. FIG. 2 is a schematic view showing an embodiment of a process for manufacturing a substrate for mounting an optical semiconductor element. The substrate for mounting an optical semiconductor element is formed by, for example, punching from a metal foil, forming a metal wiring 105 by a known method such as etching, and applying Ni / Ag plating 104 by electroplating ((a) in FIG. 2), then The metal wiring 105 is placed in a mold 151 having a predetermined shape, a thermosetting resin composition is injected from the resin injection port 150 of the mold 151, and transfer molding or compression molding is performed under predetermined conditions (FIG. 2). (B)) and can be manufactured through a step of removing the mold 151 ((c) of FIG. 2).

  In this manner, the optical semiconductor element mounting region (recessed portion) 200 is formed on the optical semiconductor element mounting substrate. The optical semiconductor element mounting region (concave portion) 200 is surrounded by the reflector 103 made of a cured product of the thermosetting resin composition. Further, the bottom surface of the recess 200 has an insulating property made of a cured product of a thermosetting resin composition provided between the metal wiring 105 serving as the first connection terminal and the metal wiring 105 serving as the second connection terminal. And a resin molded body 103 ′. For example, when the reflector is formed by transfer molding, the molding conditions are a molding temperature of 120 to 200 ° C., a molding pressure of 0.5 to 25 MPa, a post-cure temperature of 120 ° C. to 180 ° C., and a temperature of 1 to 3 at 60 to 600 seconds. Time is preferred. From the viewpoint of sufficient curing, the mold temperature is more preferably 150 to 190 ° C, and the molding pressure is more preferably 12 to 20 MPa. In addition, when the reflector is formed by compression molding, from the viewpoint of sufficient curing, the molding temperature is 120 to 200 ° C., the molding time is 30 to 600 seconds, particularly the molding temperature is 130 to 160 ° C. and the molding time is 120 to 300 seconds. It is preferable to carry out with.

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

[Optical semiconductor device]
The optical semiconductor device according to the present embodiment includes the optical semiconductor element mounting substrate and an optical semiconductor element mounted on the optical semiconductor element mounting substrate. As a more specific example, the optical semiconductor element mounting substrate, the optical semiconductor element provided in the recess of the optical semiconductor element mounting substrate, and a sealing resin portion that fills the recess and seals the optical semiconductor element And an optical semiconductor device.

  FIG. 3 is a perspective view showing 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 the optical semiconductor element mounting region (concave portion) 200 of the optical semiconductor element mounting substrate 110 and is electrically connected by the metal wiring 105 and the bonding wire 102. The 4 and 5 are schematic cross-sectional views showing an embodiment of an 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 the 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, and a metal wiring 105 on which the optical semiconductor element 100 and the Ni / Ag plating 104 are formed. Are electrically connected by a bonding wire 102 or a solder bump 107.

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

  5 and 6 show an embodiment of an optical semiconductor device in which one optical semiconductor element is provided, but two or more optical semiconductor elements may be provided in the recess.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this. For example, a molded body formed from the thermosetting resin composition according to this 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 laminated board which concerns on this embodiment is equipped with the resin layer formed using the thermosetting resin composition mentioned above, and the copper foil laminated | stacked on this resin layer.

  FIG. 7 is a schematic cross-sectional view showing a preferred embodiment of a copper clad laminate. As shown in FIG. 7, the copper-clad laminate 400 includes a base material 401, a resin layer 402 laminated on the base material 401, and a copper foil 403 laminated on the resin layer 402. Yes. Here, the resin layer 402 is formed using the thermosetting resin composition of this embodiment mentioned above. Although the base material used for a copper clad laminated board can be used without a restriction | limiting in particular as the base material 401, For example, resin laminated boards, such as an epoxy resin laminated board, and a board | substrate for optical semiconductor element mounting are mentioned.

  The copper-clad laminate 400 is produced by, for example, forming the resin layer 402 by forming the thermosetting resin composition according to the present embodiment on the surface of the substrate 401, stacking the copper foil 403, and curing by heating and pressing. can do. The formation method on the surface of the base material 401 is not limited, and examples thereof include a method of direct application and a method of laminating a resin-coated copper foil containing the thermosetting resin composition according to this embodiment by pressing or laminating. Although it does not specifically limit as conditions of heating-pressing, For example, the conditions of 130-180 degreeC, 0.5-4 MPa, and 30-600 minutes are preferable.

  Using the copper-clad laminate, a printed wiring board for an optical member such as for mounting an optical semiconductor element can be produced. The copper clad laminate 400 shown in FIG. 7 is obtained by laminating a resin layer 402 and a copper foil 403 on one side of a base material 401, but the copper clad laminate is a resin layer 402 on both sides of the base material 401. And copper foil 403 may be laminated.

  FIG. 8 is a schematic cross-sectional view showing an 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 mount optical semiconductor device including an optical semiconductor element 410 and a sealing resin 404 provided so as to seal the optical semiconductor element 410. In the optical semiconductor device 500, the optical semiconductor element 410 is bonded to the copper foil 403 through the adhesive layer 408, and is electrically connected to the copper foil 403 by the bonding wire 409.

  Furthermore, as another embodiment of the substrate for mounting an optical semiconductor element, an optical semiconductor provided with a resin layer formed between a plurality of conductor members (connection terminals) on a base material using the thermosetting resin composition described above. An element mounting substrate may be mentioned. 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 cross-sectional view showing a preferred embodiment of an optical semiconductor device. As shown in FIG. 9, the optical semiconductor device 600 includes a substrate 601, a plurality of conductor members 602 formed on the surface of the substrate 601, and a resin formed between the plurality of conductor members (connection terminals) 602. A surface-mount type optical semiconductor in which an optical semiconductor element 610 is mounted on a substrate for mounting an optical semiconductor element including a layer 603 and a transparent sealing resin 604 is provided so as to seal the optical semiconductor element 610 Device. In the optical semiconductor device 600, the optical semiconductor element 610 is bonded to the conductor member 602 through the adhesive layer 608, and is electrically connected to the conductor member 602 through a bonding wire 609. The resin layer 603 is formed using the thermosetting resin composition described above.

  As the substrate 601, a substrate used for an optical semiconductor element mounting substrate can be used without 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 photoetching a copper foil. The substrate for mounting an optical semiconductor element is formed by transfer-molding a thermosetting resin composition between a plurality of conductor members 602 on a base material 601, and heat-curing to form a resin layer 603 made of the thermosetting resin composition. Can be produced. There are no particular restrictions on the heating conditions for heat-curing the transfer-molded layer of the thermosetting resin composition, but it is preferable to perform heating under conditions of 130 to 200 ° C. and 30 to 600 minutes, for example.

  Thereafter, the resin component adhering excessively to the surface of the conductor member 602 is removed by buffing or the like to expose the circuit formed of the conductor member 602, thereby forming an optical semiconductor element mounting substrate. Moreover, in order to ensure the adhesiveness 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 or a CZ treatment (manufactured by MEC Co., Ltd.).

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to the said form. The present invention can be implemented in various modes different from the above-described embodiments 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.

(Synthesis Example 1)
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 dropped into 1000 g of water and hydrolyzed so as not to generate heat. Next, after stirring for 60 minutes under reflux conditions, the organic layer was neutralized with potassium hydroxide, and after azeotropic dehydration, a solvent such as toluene was distilled off to obtain a colorless and transparent hydrosilyl group-containing silicone resin. Mw of the obtained hydrosilyl group-containing silicone resin was 3865.

(Synthesis Example 2)
While adding 53.5 g of vinyltrimethoxysilane, 1.2 g of methyltriethoxysilane, 60 g of isopropyl alcohol, 120 g of toluene, 0.59 g of concentrated hydrochloric acid and 15.9 g of distilled water to a 500 mL flask, refluxing at 170 ° C. for 2 hours. Stir. Next, toluene was distilled off under reduced pressure to obtain an alkenyl group-containing silicone resin. Mw of the obtained alkenyl group-containing silicone resin is 2300, alkenyl group content based on the total amount of elements directly bonded to Si is 24 mol%, and based on the total amount of organic groups directly bonded to Si. The alkenyl group content was 98 mol% and the alkenyl group equivalent was 150 g / mol. The alkenyl group-containing silicone resin was stored as a 50% by mass acetone solution.

(Synthesis Example 3)
425 g of vinyltrimethoxysilane, 120 g of isopropyl alcohol, 240 g of toluene, 1.18 g of concentrated hydrochloric acid and 31.4 g of distilled water were added to a 1000 mL flask, and the mixture was stirred at 170 ° C. with refluxing for an hour. Next, toluene was distilled off under reduced pressure to obtain an alkenyl group-containing silicone resin. Mw of the obtained alkenyl group-containing silicone resin is 4000, alkenyl group content based on the total amount of elements directly bonded to Si is 25 mol%, and based on the total amount of organic groups directly bonded to Si. The alkenyl group content was 100 mol% and the alkenyl group equivalent was 85 g / mol. The alkenyl group-containing silicone resin was stored as a 50% by mass acetone solution.

(Synthesis Example 4)
A solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of both-end dimethylchlorosilane-polydimethylsiloxane and 8.5 g of methylvinyldichlorosilane in 200 g of toluene was dropped into 1000 g of water and hydrolyzed so as not to generate heat. Next, after stirring for 60 minutes under reflux conditions, the organic layer was neutralized with potassium hydroxide, and after azeotropic dehydration, a solvent such as toluene was distilled off to obtain a colorless liquid alkenyl group-containing silicone resin. Mw of the obtained alkenyl group-containing silicone resin was 3585, and the alkenyl group equivalent was 1585 g / mol.

(Synthesis Example 5)
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 were added to a 500 mL flask and refluxed at 110 ° C. for 3 hours. Stir. Next, colorless solid silicone resin was obtained by depressurizingly distilling toluene. Mw of the obtained silicone resin was 901.

(Synthesis Example 6)
Methyltriethoxysilane (142.6 g), phenyltriethoxysilane (39.7 g), isopropyl alcohol (22.8 g), toluene (22.8 g), concentrated hydrochloric acid (0.28 g) and distilled water (36 g) were added to a 500 mL flask and heated at 110 ° C. for 2.5 hours. And stirred at reflux. Next, colorless solid silicone resin was obtained by depressurizingly distilling toluene. Mw of the obtained silicone resin was 1300.

<Preparation of thermosetting resin composition for light reflection>
(Example)
According to the blending ratio (parts by mass) shown in Table 1, the respective components were blended and sufficiently kneaded and dispersed at room temperature using a roughing machine to obtain a powdery thermosetting resin composition. In addition, the thermosetting resin composition obtained in each Example was filled with a thermosetting resin composition in a mold having a metal mold having a circular through hole with a diameter of 13 mm as a mortar mold, and a saddle type It was possible to make a tablet shape at room temperature using a punch and a hand press.

(Comparative example)
According to the blending ratio (parts by mass) shown in Table 2, each component was blended and sufficiently kneaded and dispersed at room temperature using a roughing machine to obtain a powdery thermosetting resin composition.

  In addition, the compounding ratio of each component shown in each table is a value excluding the solvent, and the description part of “−” means that there is no compounding of the corresponding raw material.

The details of * 1 to 11 in Tables 1 and 2 are as follows.
* 1: Hydrosilyl group-containing silicone resin (Synthesis Example 1)
* 2: Alkenyl group-containing silicone resin (Synthesis Example 2)
* 3: Silicone resin containing alkenyl group (Synthesis Example 3)
* 4: Alkenyl group-containing silicone resin (Synthesis Example 4)
* 5: Silicone resin (Synthesis Example 5)
* 6: Silicone resin (Synthesis Example 6)
* 7: Platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex (Wako Pure Chemical Industries, Ltd., 1.7% by mass of platinum)
* 8: Fused silica (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “FB-950”, center particle size 26 μm)
* 9: Fused silica (manufactured by Admatechs Co., Ltd., trade name “SO-25R”, center particle size 1 μm)
* 10: Hollow particles (soda-lime borosilicate glass, manufactured by Sumitomo 3M Limited, trade name “S60-HS”, center particle size 27 μm)
* 11: Titanium oxide (Ishihara Sangyo Co., Ltd., trade name “CR63”, center particle size 0.2 μm)

In addition, the measuring method of each characteristic in the said synthesis example, an Example, and a comparative example is as follows.
(1) Measurement of weight average molecular weight (Mw) Mw of silicone resin is used as a GPC measuring device with pump “L-6200 type” (trade name, manufactured by Hitachi, Ltd.), columns “TSKgel-G5000HXL” and “TSKgel-G2000HXL”. ”(Trade name) manufactured by Tosoh Corporation and a detector“ L-3300RI type ”(trade name, manufactured by Hitachi, Ltd.). Measurement conditions were such that tetrahydrofuran was used as the eluent, the temperature was 30 ° C., and the flow rate was 1.0 mL / min.

(2) Measurement of alkenyl group content Using “FT-NMR AV400M” (Bruker Biospin Co., Ltd., trade name), ¹ H-NMR measurement of the silicone resin was performed, and the alkenyl group and alkyl in the silicone resin were measured. The group content was measured. As the measurement conditions, a deuterated chloroform solution adjusted to contain 0.5% by mass of a silicone resin was used, and the cumulative number (NS) was set to 32.

(3) Measurement of alkenyl group equivalent The iodine value was measured according to JIS K 0070: 1992. The alkenyl group equivalent was calculated from the measured iodine value and the weight average molecular weight measured in (1).

(4) Measurement of type D durometer heat hardness The thermosetting resin compositions obtained in the examples and comparative examples were transfer molded under the conditions of a mold temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds, A plate-shaped test piece having a thickness of 3 mm was prepared. After the obtained test piece was placed on a hot plate at 180 ° C. and allowed to stand for 10 minutes and sufficiently warmed, according to JIS K 6253-3: 2012, the type D durometer needle was pressed against the test piece, The value immediately after was measured.

(5) Measurement of breaking strength The thermosetting resin compositions obtained in the examples and comparative examples were transfer molded under the conditions of a mold temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds, and were 100 mm long × 20 mm wide. X A test piece having a thickness of 4 mm was prepared. In accordance with JIS K 7171: 2008, a three-point bending break test of the obtained test piece was performed at room temperature, and the break strength was measured.

(6) Measurement of light reflectance About the test piece produced by (4), the light reflectance in wavelength 460nm was measured using integrating sphere type spectral hardness meter CM600d (made by Konica Minolta Co., Ltd.).

  From Table 1 and Table 2, since the thermosetting resin composition of an Example has high type D durometer hardness after hardening, it is excellent in toughness, and since the white pigment is used as a pigment, after hardening Is suitable for the production of a substrate for mounting an optical semiconductor element.

  INDUSTRIAL APPLICABILITY According to the present invention, a thermosetting resin composition capable of forming a tough cured product that is less likely to crack and crack, a substrate for mounting an optical semiconductor element using the thermosetting resin composition, and a method for manufacturing the same. In addition, an optical semiconductor device can be provided.

  DESCRIPTION OF SYMBOLS 100 ... Optical semiconductor element, 101 ... Transparent sealing resin, 102 ... Bonding wire, 103 ... Reflector, 103 '... Insulating resin molding, 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 bond material, 400 ... copper-clad laminate, 401 ... substrate, 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 (13)

  A thermosetting resin composition comprising a silicone resin and a pigment comprising a hydrosilyl group-containing silicone resin and an alkenyl group-containing silicone resin having an alkenyl group equivalent of 50 to 1000 g / mol.   The thermosetting resin composition according to claim 1, wherein the alkenyl group-containing silicone resin has 75 mol% or more of alkenyl groups based on the total amount of organic groups bonded to silicon atoms.   The thermosetting resin composition according to claim 1 or 2, wherein the alkenyl group-containing silicone resin has a weight average molecular weight of 200 to 10,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein the alkenyl group-containing silicone resin has a structure represented by the following formula (I).

[Wherein, each R ¹¹ independently represents an alkenyl group. ]   The thermosetting resin composition according to any one of claims 1 to 4, comprising 0.0005 to 35 mass% of the alkenyl group-containing silicone resin based on the total amount of the thermosetting resin composition.   The thermosetting according to any one of claims 1 to 5, wherein the pigment contains at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide, and zirconium oxide. Resin composition.   The thermosetting resin composition according to any one of claims 1 to 6, wherein the pigment contains hollow particles.   The thermosetting resin composition according to any one of claims 1 to 7, which is in a tablet form.   Hardened | cured material formed from the thermosetting resin composition as described in any one of Claims 1-8.   It has a recessed part comprised from a bottom face and a wall surface, The said bottom face of the said recessed part is a mounting part of an optical-semiconductor element, The at least one part of the said wall surface of the said recessed part is as described in any one of Claims 1-8. A substrate for mounting an optical semiconductor element, comprising a molded body formed from a thermosetting resin composition. A board, and a first connection terminal and a second connection terminal provided on the board,
The optical semiconductor element mounting which has the molded object formed from the thermosetting resin composition as described in any one of Claims 1-8 between the said 1st connection terminal and the said 2nd connection terminal. Substrate.   An optical semiconductor device comprising the optical semiconductor element mounting substrate according to claim 10 and an optical semiconductor element mounted on the optical semiconductor element mounting substrate. A method of manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface,
An optical semiconductor element mounting comprising a step of forming at least a part of the wall surface of the recess by transfer molding or compression molding using the thermosetting resin composition according to any one of claims 1 to 8. Manufacturing method for industrial use.

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