JP2018145374A - Method for producing thermosetting resin composition, method for manufacturing optical semiconductor element mounting substrate, method for manufacturing optical semiconductor device, and thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a thermosetting resin composition having good moldability.SOLUTION: The method for producing a thermosetting resin composition comprises: a first step of mixing a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group to obtain a prepolymer; and a second step of mixing the prepolymer, a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and a pigment to obtain a thermosetting resin composition.SELECTED DRAWING: Figure 1

Description

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

  Thermosetting resins are used in a wide range of applications because they exhibit various excellent properties derived from their inherent cross-linked structure. 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 method for forming a reflector by transfer molding a light-reflective thermosetting resin composition containing an epoxy resin, a curing agent, a curing catalyst, a filler, and a coupling agent. . Further, Patent Document 2 discloses a resin composition for a mounting package for housing an optical semiconductor element using a silicone resin having a structure in which either one of a vinyl group or an allyl group and a hydrogen atom is directly bonded to a silicon atom. Is disclosed.

JP 2006-140207 A JP 2009-21394 A

  Although a resin composition containing a silicone resin is excellent in terms of realizing good light reflectivity, there is still room for improvement in terms of moldability.

  This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of a thermosetting resin composition provided with favorable moldability. Another object of the present invention is to provide a thermosetting resin composition having good moldability obtained by the method, a method for manufacturing a substrate for mounting an optical semiconductor element using the same, and a method for manufacturing an optical semiconductor device. To do.

  The present invention includes a first step of mixing a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group to obtain a prepolymer, a prepolymer, a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, The 2nd process of mixing a pigment and obtaining a thermosetting resin composition is related with the manufacturing method of a thermosetting resin composition.

  The present invention is also a method for manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface, wherein at least a part of the wall surface of the recess is formed of the thermosetting resin composition according to the present invention. The present invention relates to a method for manufacturing a substrate for mounting an optical semiconductor element, comprising a step of forming by transfer molding or compression molding using a thermosetting resin composition obtained by the manufacturing method.

  Furthermore, the present invention provides a light comprising a substrate, a first connection terminal and a second connection terminal provided on the substrate, and a molded body provided between the first connection terminal and the second connection terminal. A method for producing a substrate for mounting a semiconductor element, wherein at least a part of a molded body is transferred or molded using a thermosetting resin composition obtained by the method for producing a thermosetting resin composition according to the present invention. The present invention relates to a method for manufacturing a substrate for mounting an optical semiconductor element, comprising a step of forming by compression molding.

  Furthermore, the present invention is an optical semiconductor device manufacturing method comprising an optical semiconductor element mounting substrate and an optical semiconductor element mounted on the optical semiconductor element mounting substrate, wherein the optical semiconductor element mounting substrate according to the present invention is provided. It is related with the manufacturing method of an optical semiconductor device provided with the process of mounting an optical semiconductor element in the optical semiconductor element mounting board | substrate obtained by this manufacturing method.

  In still another aspect, the present invention relates to a thermosetting resin comprising a prepolymer that is a reaction product of a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group, a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and a pigment. Relates to the composition.

  According to the present invention, a method for producing a thermosetting resin composition having good moldability, a method for producing a substrate for mounting an optical semiconductor element using the same, a method for producing an optical semiconductor device, and a thermosetting resin composition are provided. 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.

[Method for producing thermosetting resin composition]
The method for producing a thermosetting resin composition according to this embodiment includes a first step of obtaining a prepolymer by mixing a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group, a prepolymer, and a hydrosilyl group. A second step of obtaining a thermosetting resin composition by mixing the containing silicone resin, the alkenyl group-containing silicone resin, and the pigment.

  According to the method for producing a thermosetting resin composition according to this embodiment, a thermosetting resin composition having good moldability can be produced. The reason why such an effect is obtained is that the present inventors particularly perform the first step, that is, the step of previously mixing a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group to form a prepolymer. I guess it is due to the provision.

  More specifically, when a molded body is produced by reacting a thermosetting resin composition containing a hydrosilyl group-containing silicone resin and an alkenyl group-containing silicone resin, due to steric hindrance, it is abrupt when reacted as it is. The reaction may occur locally, resulting in an unreacted portion of the hydrosilyl group. When unreacted hydrosilyl groups are present, the hardness of the molded product is lowered, and the hydrosilyl group portion sticks to the molding die, thereby causing mold contamination. Mold dirt reduces workability and deteriorates moldability. Also, curing before the resin composition is sufficiently filled in the mold due to a rapid reaction can be one factor that deteriorates moldability.

  On the other hand, as described above, in the first step, a part of the hydrosilyl group is reacted with an alkenyl group in advance to form a prepolymer, thereby realizing a milder reaction than in the past in molding a resin composition. Therefore, it is considered that local reactions can be prevented. Moreover, since the time (gel time) until a resin composition hardens | cures becomes long, the filling property to the inside of a metal mold | die improves, As a result, it is thought that favorable moldability can be ensured.

Hereinafter, each step will be described in detail.
<First step>
The first step is a step of obtaining a prepolymer by mixing a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group.

(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 in which a hydrogen atom is directly bonded to a silicon atom (Si—H). For example, a hydrosilyl group-containing silicone oil may be used.

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 easy synthesis of the hydrosilyl group-containing silicone resin and the point that a solid is easily obtained at 25 ° C., 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. Examples of the hydrocarbon group include the same groups as the hydrocarbon groups described above. 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 further improving the moldability of the thermosetting resin composition, it is preferably 200 or more, more preferably 1000 or more, and 1500 or more. And more preferred. On the other hand, the weight average molecular weight of the hydrosilyl group-containing silicone compound is preferably 15000 or less, more preferably 10,000 or less, and further preferably 7000 or less, from the viewpoint of 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 1500 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

(Silicon compound having an alkenyl group)
The silicon compound having an alkenyl group is not particularly limited as long as it has an alkenyl group and a silicon atom. The alkenyl group may or may not be directly bonded 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. As the compound having an alkenyl group, a low molecular compound such as a silane compound having an alkenyl group may be used, or a polymer compound such as a silicone resin having an alkenyl group (alkenyl group-containing silicone resin) may be used.

As the silane compound having an alkenyl group, for example, a compound represented by the following formula (A) may be used.
_{X 3-n Me n Si-} Y (A)
In the formula (A), X represents an alkoxy group having 1 to 10 carbon atoms or a halogen atom, preferably a methoxy group, an ethoxy group, a methoxyethoxy group or a chlorine atom. Me represents a methyl group. Y represents a group containing an alkenyl group, and is preferably a vinyl group, an acryloyl group or a methacryloyl group. n represents an integer of 0 to 3.

  Examples of the compound represented by the formula (A) include methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltri Mention may be made of methoxysilane, vinylmethyldimethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltriphenoxysilane, vinyltrichlorosilane and vinylmethyldichlorosilane. Among these, vinyltriethoxysilane, vinyltrimethoxysilane, or vinylmethyldimethoxysilane may be used.

  Examples of the silane compound having an alkenyl group other than the compound represented by the formula (A) include vinyl trimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. And divinyltetramethyldisilazane.

  The alkenyl group-containing silicone resin is not particularly limited as long as it is a compound having a main skeleton formed by a siloxane bond and an alkenyl group, and may be, for example, an alkenyl group-containing silicone oil. The alkenyl group can be introduced into the silicone resin using, for example, a silane compound having an alkenyl group.

  The alkenyl group-containing silicone resin may have 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 improved, and a tough cured product is more easily formed.

Examples of the silicone resin having a ladder structure include a resin 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 ). You may have a structure.

  The silicone resin having a ladder structure preferably has a structure represented by the formula (I) continuously. In this case, for example, the silicone resin can have a structure represented by the following formula (I ′). 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 siloxane skeleton has the structure represented by the formula (I) continuously, 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 an alkenyl group in the molecule. 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 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 1000 or more, and 1500 or more from the viewpoint of further improving the moldability of the thermosetting resin composition. And more 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 15000 or less, more preferably 10,000 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 15000, 1000 to 10000, or 1500 to 7000.

(Prepolymer)
The prepolymer can be prepared by mixing the above-described hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group, and is a reaction product of the hydrosilyl group-containing silicone resin and the silicon compound having an alkenyl group.

  Although the method for producing the prepolymer is not particularly limited, for example, the reaction temperature is preferably 10 to 80 ° C. and more preferably 15 to 60 ° C. in order to cause the hydrosilyl group and the alkenyl group to react gently. More preferably, it is 20-40 degreeC.

  When mixing the hydrosilyl group-containing silicone resin and the silicon compound having an alkenyl group, a solvent may be used from the viewpoint of easy mixing work. The type of the solvent is not particularly limited. For example, 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; Ether solvents; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents including amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atoms including sulfoxide solvents such as dimethyl sulfoxide Examples of the solvent include ester solvents including a lactone solvent such as γ-butyrolactone. From the viewpoint of solubility of the hydrosilyl group-containing silicone resin and the silicon compound having an alkenyl group, the solvent may be an alcohol solvent, a ketone solvent, or a nitrogen atom-containing solvent, from the viewpoint of ease of solvent removal. , Acetone or tetrahydrofuran.

  The mixing ratio of the hydrosilyl group-containing silicone resin and the silicon compound having an alkenyl group is, for example, 10-60 with respect to 1 mol of the alkenyl group of the hydrosilyl group of the hydrosilyl group-containing silicone resin of the alkenyl group-containing silicon compound. It is preferable to mix so that it may become mol, It is more preferable to mix so that it may become 12-50 mol, It is still more preferable to mix so that it may become 15-35 mol. By setting the mixing ratio within the above numerical range, a rapid reaction between the hydrosilyl group-containing silicone resin and the silicon compound having an alkenyl group can be suppressed, and the thermosetting resin composition obtained in the second step to be described later In addition to reducing mold contamination caused by the above, moldability can be further improved.

  The weight average molecular weight (Mw) of the prepolymer is not particularly limited, but is preferably 10,000 or more, more preferably 12,000 or more, and further preferably 15,000 or more from the viewpoint of further improving moldability. The Mw of the prepolymer is preferably 90000 or less, more preferably 80000 or less, and further preferably 70000 or less from the viewpoint of improving reactivity. That is, the Mw of the prepolymer is preferably 10,000 to 90,000, more preferably 12000 to 80000, and even more preferably 15000 to 70000.

  The amount of the hydrosilyl group-containing silicone resin used in the first step is the amount of the hydrosilyl group-containing silicone resin used in the first step and the second step described later from the viewpoint of easy control of the reaction rate. Is preferably 10 to 80 parts by mass and more preferably 15 to 75 parts by mass with respect to 100 parts by mass in total with the amount of the hydrosilyl group-containing silicone resin used. From the same viewpoint, the amount of the silicon compound having an alkenyl group used in the first step is 100 mass in total with the amount of the silicon compound and the alkenyl group-containing silicone resin used in the second step described later. The amount is preferably 10 to 80 parts by mass, and more preferably 15 to 75 parts by mass with respect to parts.

(Curing catalyst)
In the first step, it is preferable to further use a curing catalyst from the viewpoint of reactivity. As a curing catalyst, the thing similar to the curing catalyst used in the 2nd process mentioned later can be used. The amount (mixing ratio) of the curing catalyst used in the first step is not particularly limited, but the entire amount or only a part of the curing catalyst used in the second step may be used. From the viewpoint of sufficiently controlling the reaction rate and the molecular weight of the resulting prepolymer, the amount (mixing ratio) of the curing catalyst used in the first step is the total amount of the silicon compound having a hydrosilyl group-containing silicone resin and an alkenyl group being 100. 0.001 to 0.1 parts by mass with respect to parts by mass, preferably 0.001 to 0.08 parts by mass, more preferably 0.005 to 0.07 parts by mass, It is especially preferable that it is 0.008-0.05 mass part.

<Second step>
The second step is a step of obtaining a thermosetting resin composition by mixing the prepolymer obtained in the first step, a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and a pigment. .

(Prepolymer)
The prepolymer used in the second step is the prepolymer obtained in the first step, and a duplicate description is omitted here. Although the content (mixing ratio) of the prepolymer in the second step is not particularly limited, for example, 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of hydrosilyl group-containing silicone resin and alkenyl group-containing silicone resin described later. It is preferable, it is more preferable in it being 20-75 mass parts, and it is still more preferable in it being 25-70 mass parts. If content of a prepolymer is in the said range, the moldability of the obtained thermosetting resin composition will improve further, and the resin stain | pollution | contamination at the time of shaping | molding can further be reduced.

(Hydrosilyl group-containing silicone resin)
It does not specifically limit as a hydrosilyl group containing silicone resin used in a 2nd process, For example, you may use the hydrosilyl group containing silicone resin illustrated at the said 1st process. The hydrosilyl group-containing silicone resin used in the second step may be the same as or different from the hydrosilyl group-containing silicone resin used in the first step.

  The content of the hydrosilyl group-containing silicone resin in the second step is not particularly limited, but from the viewpoint of further improving the moldability of the thermosetting resin composition, 0.01 to 40% by mass based on the total amount of the resin composition. Is preferable, 0.1 to 35% by mass is more preferable, and 1.0 to 30% by mass is further preferable.

(Alkenyl group-containing silicone resin)
The alkenyl group-containing silicone resin used in the second step is not particularly limited, and for example, the same alkenyl group-containing silicone resin exemplified in the first step may be used. The alkenyl group-containing silicone resin used in the second step may be the same as or different from the alkenyl group-containing silicone resin used in the first step.

  Although content in particular of the alkenyl group containing silicone resin in a 2nd process is not restrict | limited, From a viewpoint of further improving the moldability of a thermosetting resin composition, 0.01-40 mass% on the basis of the resin composition whole quantity. Is preferable, 0.1 to 35% by mass is more preferable, and 1.0 to 30% by mass is further preferable.

(Pigment)
A pigment adds the color according to a use to the hardened | cured material of the thermosetting resin composition which concerns on 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.

(Curing catalyst)
From the viewpoint of reactivity, the thermosetting resin composition according to this 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 (mixing ratio) of the curing catalyst contained in the thermosetting resin composition is not particularly limited. For example, from the viewpoint of further improving the curability of the thermosetting resin composition, hydrosilyl group-containing silicone resin and alkenyl 0.005-0.5 mass part is preferable with respect to 100 mass parts of total amounts with group-containing silicone resin, 0.01-0.3 mass part is more preferable, 0.01-0.2 mass part is Further preferred. Further, the amount of the curing catalyst with respect 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, it is 0.08 to 2.2 ppm.

(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 (fused spherical silica, crushed silica, etc.), antimony oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate and the like.

  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.

  The spiral flow of the thermosetting resin composition of the present embodiment is preferably 40 to 180 cm, more preferably 50 to 150 cm, from the viewpoint of securing the filling property to the mold at a higher level. More preferably, it is 60-100 cm. The spiral flow of the thermosetting resin composition can be measured, for example, by the method described in the examples described later.

  When the thermosetting resin composition of this embodiment is cured, the gel time (time until the composition loses fluidity and becomes a gel state) is, for example, 165 ° C. from the viewpoint of further improving moldability. It is preferable that it is 10 to 60 seconds in this environment. The gel time of a thermosetting resin composition can be measured by the method described in the below-mentioned Example, for example.

  In the second step, the method of mixing the various components exemplified above is not particularly limited, and for example, the following kneading step and pulverizing step may be provided.

(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. If 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 if it is within 40 minutes, it is easy to control the high molecular weight of the resin composition and molding. It can suppress more that a resin composition hardens before.

  The thermosetting resin composition that has been subjected to the kneading step is preferably in a state in which dry pulverization described later can be performed. Therefore, you may provide the process (cooling process) which cools the thermosetting resin composition which performed the kneading | mixing process as needed before the below-mentioned crushing process.

(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. In this way, a powdery thermosetting resin composition can be obtained.

  In the manufacturing method of the thermosetting resin composition which concerns on this embodiment, it is preferable to further provide the 3rd process processed into a tablet shape after said 2nd process. 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 columnar 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 becomes better. 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 the 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.

  The method for coating the adherend with the filler is not particularly limited as long as it can be brought into contact with the tablet-like thermosetting resin composition. 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.

  The thermosetting resin composition of this embodiment mentioned above can form hardened | cured material by thermosetting. Although the conditions of thermosetting are not specifically limited, For example, it can harden | cure by heating at the temperature of 170-200 degreeC for 60-300 seconds. You may perform thermosetting as a part of process included in the below-mentioned shaping | molding method.

[Method for manufacturing substrate for mounting optical semiconductor element]
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 Further, the bottom surface of the recess includes a first connection terminal and a second connection terminal, and a molded body provided therebetween, and at least a part of the molded body is the thermosetting resin composition of the present embodiment. It consists of a molded body formed from a product.

  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.

[Method for Manufacturing Optical Semiconductor Device]
The optical semiconductor device according to this embodiment can be manufactured by mounting a semiconductor element on the optical semiconductor element mounting substrate obtained above. As a more specific example of the semiconductor device, the optical semiconductor element mounting substrate, the optical semiconductor element provided in the concave portion of the optical semiconductor element mounting substrate, and a seal that fills the concave portion and seals the optical semiconductor element. An optical semiconductor device provided with a stop resin part is mentioned.

  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.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

(Synthesis Example 1)
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 1600.

(Synthesis Example 2)
A solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of both terminal dimethylchlorosilane-polydimethylsiloxane and 6.9 g of methyldichlorosilane in toluene was dropped into 1000 g of water so as not to generate heat and hydrolyzed. 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 1400.

(Synthesis Example 3)
A solution prepared by dissolving 666.8 g of phenyltrichlorosilane, 278.6 g of dimethylchlorosilane-polydimethylsiloxane at both ends and 40.3 g of methyldichlorosilane in toluene was dropped into 3000 g of water for hydrolysis. 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 synthesize a colorless and transparent hydrosilyl group-containing silicone resin. Mw of the obtained hydrosilyl group-containing silicone resin was 2000.

(Synthesis Example 4)
A solution prepared by dissolving 666.8 g of phenyltrichlorosilane, 278.6 g of both ends dimethylchlorosilane-polydimethylsiloxane, and 31.6 g of dimethylchlorosilane in toluene was dropped into 3000 g of water for hydrolysis. 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 synthesize a colorless and transparent hydrosilyl group-containing silicone resin. Mw of the obtained hydrosilyl group-containing silicone resin was 3000.

(Synthesis Example 5)
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. for 3 hours while refluxing. Subsequently, toluene was distilled off under reduced pressure to obtain an alkenyl group-containing silicone resin. Mw of the obtained alkenyl group-containing silicone resin was 2400.

[Preparation of thermosetting resin composition for light reflection]
(Examples 1-5)
<First Step: Preparation of Prepolymer>
According to the blending ratio (parts by mass) shown in Table 1, each component was blended, and prepolymers 1 to 5 were obtained by sufficiently kneading and dispersing at room temperature using a rough machine. Mw of the obtained prepolymers 1 to 5 is shown in Table 1.

<Second step: Preparation of thermosetting resin composition>
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 white resin composition.

(Comparative Examples 1-5)
According to the blending ratio (parts by mass) shown in Table 3, each component is blended at one time without being prepolymerized, and is sufficiently kneaded and dispersed at room temperature using a rough machine to form a powdery thermosetting white resin composition. Got.

In Tables 1, 2, and 3, details of * 1 to * 12 are as follows.
* 1: Hydrosilyl group-containing silicone resin (Synthesis Example 3)
* 2: Hydrosilyl group-containing silicone resin (Synthesis Example 4)
* 3: Hydrosilyl group-containing silicone resin (Momentive Performance Materials, trade name “TSF484”)
* 4: Silicon compound having an alkenyl group (product name “XC96-C0214” manufactured by Momentive Performance Materials, Inc.)
* 5: Silicon compound having an alkenyl group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-1003”)
* 6: Alkenyl group-containing silicone resin (Synthesis Example 5)
* 7: Silicone resin containing alkenyl group (Synthesis Example 1)
* 8: Hydrosilyl group-containing silicone resin (Synthesis Example 2)
* 9: Titanium oxide (Ishihara Sangyo Co., Ltd., trade name “CR63”, center particle size 0.2 μm)
* 10: Platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex (Wako Pure Chemical Industries, Ltd., 1.7% by mass of platinum)
* 11: Fused spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “FB-950”, center particle size 26 μm)
* 12: Fused spherical silica (manufactured by Admatechs, trade name “SO-25R”, center particle size 1 μm)

  In addition, the measuring method of each characteristic in the said synthesis example, an Example, and a comparative example is as follows.

(Measurement of weight average molecular weight (Mw))
Mw as a GPC measuring device pump “L-6200 type” (trade name, manufactured by Hitachi, Ltd.), column “TSKgel-G5000HXL” and “TSKgel-G2000HXL” (trade name, manufactured by Tosoh Corporation) and detector “ It measured using "L-3300RI type" (The Hitachi, Ltd. make, brand name). 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.

(Measurement of moldability)
As a mold for measuring moldability, a mold composed of an upper mold and a lower mold having a recess and a resin inlet for forming a disk-shaped molded product having a diameter of 20 mm and a thickness of 2 mm was used. . Using the thermosetting resin composition prepared in each Example and each Comparative Example, transfer molding was performed under the conditions of a mold temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds, and a test piece was molded. The presence or absence of an unfilled portion was confirmed by visually observing the test piece. The evaluation results were “A” when no unfilled portion was seen and “B” when an unfilled portion was seen.

(Measurement of gelation time)
Using a gelling tester, an appropriate amount (about 3 g) of the thermosetting resin composition obtained in each example and each comparative example was dropped on a hot plate at 165 ° C. until the gelled state was lost. Was measured.

(Measurement of spiral flow)
In accordance with the spiral flow evaluation method “EMMI-1-66”, the thermosetting resin composition prepared in each example and each comparative example was molded under predetermined conditions using a spiral flow measurement mold. The flow distance (cm) of the resin composition at that time was measured.

(Measurement of light reflectance)
The thermosetting resin composition prepared in each example and each comparative example was transfer molded under the conditions of a mold temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds to prepare a plate-shaped test piece having a thickness of 3 mm. About the produced test piece, the light reflectance in wavelength 46nm was measured using integrating sphere type | mold spectrocolorimeter CM600d (made by Konica Minolta Co., Ltd.).

  According to Examples and Comparative Examples, it can be seen that when a part of the silicone resin is prepolymerized in advance, the moldability is excellent as compared with the case where it is not prepolymerized. Moreover, in an Example, the gelation time is longer than a comparative example, and the value of spiral flow is large. For these reasons, the thermosetting resin composition according to the present invention can reduce the occurrence of unfilled portions due to rapid curing during transfer molding.

  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 (10)

A first step of mixing a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group to obtain a prepolymer;
A second step of mixing the prepolymer, a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and a pigment to obtain a thermosetting resin composition;
A method for producing a thermosetting resin composition.   The method of claim 1, wherein the prepolymer has a weight average molecular weight of 10,000 to 90,000.   In the first step, the hydrosilyl group-containing silicone resin is mixed so that the hydrosilyl group has a molar ratio of 10 to 60 mol with respect to 1 mol of the alkenyl group of the silicon compound. The method described in 1.   The mixing ratio of the prepolymer in the second step is 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the hydrosilyl group-containing silicone resin and the alkenyl group-containing silicone resin. 4. The method according to any one of 3.   The method according to any one of claims 1 to 4, wherein the pigment contains at least one selected from the group consisting of titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide, zirconium oxide, and hollow particles.   The method as described in any one of Claims 1-5 further provided with the 3rd process of processing the said thermosetting resin composition into a tablet form. A method of manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface,
It 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 obtained by the method according to any one of claims 1 to 6. And manufacturing method of substrate for mounting optical semiconductor element. An optical semiconductor device comprising: a substrate; a first connection terminal and a second connection terminal provided on the substrate; and a molded body provided between the first connection terminal and the second connection terminal. A method for manufacturing a mounting substrate, comprising:
An optical device comprising a step of forming at least a part of the molded body by transfer molding or compression molding using the thermosetting resin composition obtained by the method according to any one of claims 1 to 6. A method for manufacturing a substrate for mounting semiconductor elements. An optical semiconductor device manufacturing method comprising: an optical semiconductor element mounting substrate; and an optical semiconductor element mounted on the optical semiconductor element mounting substrate,
A method for manufacturing an optical semiconductor device, comprising a step of mounting the optical semiconductor element on a substrate for mounting an optical semiconductor element obtained by the method according to claim 7 or 8.   A thermosetting resin composition comprising a prepolymer that is a reaction product of a hydrosilyl group-containing silicone resin and a silicon compound having an alkenyl group, a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and a pigment.

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