JP6988107B2 - A method for manufacturing a thermosetting resin composition, a method for manufacturing a substrate for mounting an optical semiconductor device, a method for manufacturing an optical semiconductor device, and a thermosetting resin composition. - Google Patents

Description

The present invention relates to a method for manufacturing a thermosetting resin composition, a method for manufacturing a substrate for mounting an optical semiconductor device, a method for manufacturing 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 unique crosslinked structure. In recent years, as one of the applications, optical semiconductor devices that combine optical semiconductor elements such as LEDs (Light Emitting Diodes) with phosphors have advantages such as high energy efficiency and long life, and are used for outdoor displays and portable devices. It is applied to various applications such as liquid crystal backlights and in-vehicle applications, and its demand is expanding.

As one kind of optical semiconductor device, a surface mount type optical semiconductor device can be mentioned. Some surface-mounted optical semiconductor devices have an optical semiconductor element and a reflector (reflecting unit) provided so as to surround the optical semiconductor element. Patent Document 1 discloses a method of forming a reflector by transfer molding a thermosetting resin composition for light reflection containing an epoxy resin, a curing agent, a curing catalyst, a filler and a coupling agent. .. Further, Patent Document 2 describes a resin composition for a mounting package for storing an optical semiconductor device using a silicone resin having a structure in which either a vinyl group or an allyl group and a hydrogen atom are directly bonded to a silicon atom. Is disclosed.

Japanese Unexamined Patent Publication No. 2006-140207 Japanese Unexamined Patent Publication No. 2009-21394

Although the resin composition containing a silicone resin is excellent in that it can realize good light reflectivity, there is still room for improvement in terms of moldability.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a thermosetting resin composition having good 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 device using the same, and a method for manufacturing an optical semiconductor device. do.

The present invention comprises 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, and an alkenyl group-containing silicone resin. The present invention relates to a method for producing a thermosetting resin composition, comprising a second step of mixing with a pigment to obtain 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 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, which comprises a step of forming by transfer molding or compression molding using a thermosetting resin composition obtained by the manufacturing method.

Further, the present invention comprises 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 substrate for mounting a semiconductor element, wherein at least a part of a molded product is transfer molded or transferred using the thermosetting resin composition obtained by the method for manufacturing 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, which comprises a step of forming by compression molding.

Further, the present invention is a method for manufacturing an optical semiconductor device including 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 described above. The present invention relates to a method for manufacturing an optical semiconductor device, comprising a step of mounting the optical semiconductor element on a substrate for mounting the optical semiconductor element obtained by the above-mentioned manufacturing method.

In yet another aspect, the present invention is a thermosetting resin containing a prepolymer which 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. Regarding the composition.

According to the present invention, a method for manufacturing a thermosetting resin composition having good moldability, a method for manufacturing a substrate for mounting an optical semiconductor device using the same, a method for manufacturing 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 substrate for mounting an optical semiconductor element. It is a schematic diagram which shows one Embodiment of the process of manufacturing the substrate for mounting an optical semiconductor element. It is a perspective view which shows one Embodiment of the state which the optical semiconductor element is mounted on the substrate for mounting an optical semiconductor element. It is a schematic cross-sectional view which shows one Embodiment of an optical semiconductor device. It is a schematic cross-sectional view which shows the other embodiment of an optical semiconductor device. It is a schematic cross-sectional view which shows the other embodiment of an optical semiconductor device. It is a schematic cross-sectional view which shows one Embodiment of a copper-clad laminated board. It is a schematic cross-sectional view which shows an example of the optical semiconductor device manufactured using the copper-clad laminate. It is a schematic cross-sectional view which shows the 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.

[Manufacturing method of thermosetting resin composition]
The method for producing a thermosetting resin composition according to the present embodiment 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, and a hydrosilyl group. The present invention comprises a second step of mixing the contained silicone resin, the alkenyl group-containing silicone resin, and the pigment to obtain a thermosetting resin composition.

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

More specifically, when a thermosetting resin composition containing a hydrosilyl group-containing silicone resin and an alkenyl group-containing silicone resin is reacted to produce a molded product, the reaction is rapid if the reaction is carried out as it is due to steric hindrance. Reactions may occur locally, resulting in unreacted moieties of hydrosilyl groups. When an unreacted hydrosilyl group is present, the hardness of the molded product is lowered, and the hydrosilyl group portion sticks to the molding die, which causes stains on the mold. Mold stains reduce workability and deteriorate moldability. Further, curing before the resin composition is sufficiently filled in the mold due to a rapid reaction may be one factor of deteriorating the moldability.

On the other hand, as described above, by reacting a part of the hydrosilyl group with the alkenyl group in advance to form a prepolymer in the first step, a milder reaction than before is realized in the subsequent molding of the resin composition. Therefore, it is considered that it is possible to prevent a local reaction from occurring. Further, it is considered that the time until the resin composition is cured (gel time) becomes long, so that the filling property into the inside of the mold is improved, and as a result, good moldability can be ensured.

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

(Silicone resin containing hydrosilyl group)
The hydrosilyl group-containing silicone resin is not particularly limited as long as it is a silicone resin having a hydrosilyl group, which is a group (Si—H) in which a hydrogen atom is directly bonded to a silicon atom, and 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.} can.

Structural units having a hydrosilyl group include, for example, methylmethoxydisilane, dimethoxydisilane, methoxytrisilane, ethylmethoxydisilane, dimethylethoxysilane, propyldiethoxysilane, propylethoxydisilane, n-butyldimethoxysilane, phenyldimethoxysilane, phenylmethoxy. Ekoxyhydroxysilanes such as disilane and triethoxysilane; methyldichlorosilane, n-propyldichlorosilane, isopropyldichlorosilane (1,1-dichloro-2-methyl-1-silapropane), n-butyldichlorosilane, n-pentyldi Alkyldichlorosilane such as chlorosilane, cyclopentyldichlorosilane, and cyclohexyldichlorosilane can be used and introduced into the silicone resin.

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 the 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, and from the viewpoint of easiness 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 easiness 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 and the like. As the organic group, an aryl group is preferable, and a phenyl group is more preferable, from the viewpoint of easiness of synthesizing the hydrosilyl group-containing silicone resin and the fact that a solid can be easily obtained at 25 ° C.

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. units represented by ^_2/2, may have at least one unit selected from units represented by the unit and _{SiO 4/2} represented by R _{3 SiO 1/2.}

R ¹ , R ² and R ³ each independently represent a monovalent organic group, and are preferably hydrocarbon groups having 1 to 12 carbon atoms from the viewpoint of availability. As the hydrocarbon group, a group similar to the above-mentioned hydrocarbon group is exemplified. For 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 is preferably 200 or more, more preferably 1000 or more, and more preferably 1500 or more from the viewpoint of further improving the moldability of the thermosetting resin composition. Is even more preferable. On the other hand, the weight average molecular weight of the hydrosilyl group-containing silicone compound is preferably 15,000 or less, more preferably 10,000 or less, and further preferably 7,000 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 10000, or 1500 to 7000.

The weight average molecular weight Mw in the present specification is obtained by measuring under the following conditions using a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
(GPC condition)
Pump: L-6200 type (manufactured by Hitachi, Ltd., product name)
Columns: TSKgel-G5000HXL and TSKgel-G2000HXL (manufactured by Tosoh Corporation, trade name)
Detector: L-3300RI type (manufactured by Hitachi, Ltd., product 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. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group and a 2-pentenyl group. 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 weight compound such as a silane compound having an alkenyl group may be used, or a high molecular weight 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 or a halogen atom having 1 to 10 carbon atoms, and is 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, 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, and vinyltri. Examples thereof include methoxysilane, vinylmethyldimethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltriphenoxysilane, vinyltrichlorosilane and vinylmethyldichlorosilane. Among them, 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 vinyltrimethylenedioxysilane, 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 due to 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 by using, for example, a silane compound having an alkenyl group.

The alkenyl group-containing silicone resin may have a ladder-type structure as a siloxane skeleton. The ladder-type 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-shaped structure, the crosslink density of the thermosetting resin composition after curing is further improved, and it becomes easier to form a tough cured product.

Examples of the silicone resin having a ladder-type 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. The following formula (I) is understood to have the above-mentioned structural unit and two oxygen atoms connecting the structural units, and the silicone resin having a ladder-type structure is represented by ^{(R 11} SiO _3/2). It may have a structure.

The silicone resin having a ladder-type structure preferably has a continuous structure represented by the formula (I), and in that case, for example, it can have a structure represented by the following formula (I'). In the following formula (I'), three sets of constituent units, two sets of two oxygen atoms connecting them, and two oxygen atoms connecting two adjacent structural units (not shown) on the right side are 1 set. It is understood that it has a set.

When the siloxane skeleton has a continuous structure represented by the formula (I), the number of repeating units of the structure represented by the formula (I) is not particularly limited, but from the viewpoint of further improving the cross-linking density after curing, it is 3 to 5000. It is preferably 5 to 3000, more preferably 10 to 2000.

The alkenyl group-containing silicone resin may have a group other than the alkenyl group in the molecule. Examples of the structural unit having a group other than the 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 be doing it. R ⁴ and R ⁵ each independently represent a monovalent organic group, and are preferably hydrocarbon groups having 1 to 12 carbon atoms from the viewpoint of availability. Examples of the hydrocarbon group include the same hydrocarbon groups as those ^{of R 1} , R ² and R ^{3 described above.}

The alkenyl group-containing silicone resin preferably has 22 mol% or more, more preferably 23 mol% or more, still more preferably 24 mol% or more, based on the total amount of the 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 hard to crack, and the automatic transportability during continuous molding is further improved. The upper limit of the amount of the alkenyl group 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 more preferably 1500 or more from the viewpoint of further improving the moldability of the thermosetting resin composition. Is even more preferable. The weight average molecular weight of the alkenyl group-containing silicone resin is preferably 15,000 or less, more preferably 10,000 or less, and even more preferably 7,000 or less, from the viewpoint of further improving the hardness of the cured product. 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 produced by mixing the above-mentioned 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.

The method for producing the prepolymer is not particularly limited, but for example, the reaction temperature is preferably 10 to 80 ° C, more preferably 15 to 60 ° C in order to gently react the hydrosilyl group and the alkenyl group. It is more preferably 20 to 40 ° C.

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 ease of mixing work. The type of solvent is not particularly limited, and is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether-based solvent; Aromatic solvent such as toluene, xylene, mesityrene; Nitrogen atom-containing solvent containing amide-based solvent such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Sulfur atom-containing solvent containing sulfoxide-based solvent such as dimethylsulfoxide Solvent; Examples thereof include an ester solvent containing 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-based solvent, a ketone-based solvent or a nitrogen atom-containing solvent, and 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 to 60 for the hydrosilyl group of the hydrosilyl group-containing silicone resin with respect to 1 mol of the alkenyl group of the alkenyl group-containing silicon compound. It is preferable to mix them to be mol, more preferably 12 to 50 mol, and even more preferably 15 to 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 described later can be suppressed. It is possible to reduce the stain on the mold due to the above, and further improve the moldability.

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 90,000 or less, more preferably 80,000 or less, and further preferably 70,000 or less, from the viewpoint of improving the reactivity. That is, the Mw of the prepolymer is preferably 1000 to 90000, more preferably 12000 to 80000, and even more preferably 1500 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. It is preferably 10 to 80 parts by mass, and more preferably 15 to 75 parts by mass with respect to 100 parts by mass of the total amount with the amount of the hydrosilyl group-containing silicone resin used in. 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.

(Curing catalyst)
In the first step, it is preferable to further use a curing catalyst from the viewpoint of reactivity. As the curing catalyst, the same curing catalyst as that used in the second step described 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 obtained prepolymer, the amount (mixing ratio) of the curing catalyst used in the first step is 100, which is the total amount of the hydrosilyl group-containing silicone resin and the silicon compound having an alkenyl group. It is preferably 0.001 to 0.1 parts by mass, more preferably 0.001 to 0.08 parts by mass, still more preferably 0.005 to 0.07 parts by mass, based on parts by mass. It is particularly preferably 0.008 to 0.05 parts by mass.

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

(Prepolymer)
The prepolymer used in the second step is the prepolymer obtained in the first step, and redundant description will be omitted here. The content (mixing ratio) of the prepolymer in the second step is not particularly limited, and is, for example, 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 described later. It is preferably 20 to 75 parts by mass, more preferably 25 to 70 parts by mass. When the content of the prepolymer is within the above range, the moldability of the obtained thermosetting resin composition is further improved, and the resin stain at the time of molding can be further reduced.

(Silicone resin containing hydrosilyl group)
The hydrosilyl group-containing silicone resin used in the second step is not particularly limited, and for example, the hydrosilyl group-containing silicone resin exemplified in the first step may be used. 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. It is preferably 0.1 to 35% by mass, more preferably 1.0 to 30% by mass, and even more preferably 1.0 to 30% by mass.

(Silicone resin containing alkenyl group)
The alkenyl group-containing silicone resin used in the second step is not particularly limited, and for example, the same as the 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.

The content of the alkenyl 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. It is preferably 0.1 to 35% by mass, more preferably 1.0 to 30% by mass, and even more preferably 1.0 to 30% by mass.

(Pigment)
The pigment adds a color according to the application to the cured product of the thermosetting resin composition according to the present embodiment. The pigment according to the present embodiment can be selected according to the intended use of the cured product of the thermosetting resin composition to be produced. Examples of the pigment include white pigment, black pigment, red pigment, yellow pigment, orange pigment, purple (菫) color pigment, blue pigment and 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 the red pigment include lead tan, iron oxide red, quinacridone, diketopyrrolopyrrole, anthraquinone, perylene, perinone and indigoid. Examples of the yellow pigment include chrome yellow and zinc yellow. Examples of the blue pigment include ultramarine blue, Prussian blue (ferrocyanine potassium potassium), phthalocyanine blue, anthraquinone and indigoid. Examples of the orange pigment include diketopyrrolopyrrole, perylene, anthraquinone, perinone, quinacridone and indigoid. Examples of the purple (violet) pigment 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 the thermosetting resin composition is required to have light reflection characteristics, it is preferable to use a white pigment as the pigment. Since the thermosetting resin composition contains a white pigment, the cured product of the thermosetting resin composition has excellent reflectance, and when used as a light reflecting material provided on a substrate for mounting an optical semiconductor device. 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, zirconium oxide and the like, and titanium oxide, alumina and zinc oxide are preferable from the viewpoint of obtaining better light reflectivity. These may be used alone or in combination of two or more.

Hollow particles may be used as the white pigment. The hollow particles are particles having voids 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 on the surface and inner walls. 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, and specifically, for example, soda glass silicate. , Aluminum silicate glass, borosilicate soda glass, silus particles and the like. As the organic hollow particles, a polystyrene-based resin, a poly (meth) acrylate-based resin, and a crosslinked product thereof can be preferably used. From the viewpoint of heat resistance and pressure resistance, the outer shell of the hollow particles is at least one selected from the group consisting of sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, silas, crosslinked styrene resin, and crosslinked acrylic resin. It is preferable that it is composed of the above materials.

When a 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. It is more preferably in the range. When the central particle size 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 characteristic of the cured product becomes better. The central particle size can be obtained as the _{mass average value D 50} (or median diameter) in the particle size distribution measurement by the laser optical diffraction method.

The content of the pigment 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, and more preferably 10 to 80% based on the total amount of the resin composition. More preferably, it is by mass. When a white pigment is used, when the content is 1% by mass or more, the light reflection characteristics of the cured product are further improved, and when the content 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 100 to 1500 parts by mass with respect to 100 parts by mass of the total amount of the silicone resin. It is more preferably a part.

(Curing catalyst)
From the viewpoint of reactivity, it is preferable that the thermosetting resin composition according to the present embodiment contains a curing catalyst that promotes the hydrosilylation reaction of the silicone resin. Examples of the curing catalyst include a casted catalyst; a single platinum; a carrier (alumina, silica, carbon black, etc.) on which solid platinum is supported; platinum chloride acid; a complex of platinum chloride acid with alcohol, aldehyde, ketone, etc. Platinum-olefin complex; platinum-vinylsiloxane complex; platinum-phosphine complex; platinum-phosphite complex and dicarbonyldichloroplatinum. These curing catalysts may be used alone or in combination of two or more.

Examples of the platinum-olefin complex include Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ and Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ . 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. Can be 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, platinum chloride acid, platinum-olefin complex or 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, but for example, from the viewpoint of further improving the curability of the thermosetting resin composition, the hydrosilyl group-containing silicone resin and the alkenyl. 0.005 to 0.5 parts by mass is preferable, 0.01 to 0.3 parts by mass is more preferable, and 0.01 to 0.2 parts by mass is preferable with respect to 100 parts by mass of the total amount of the group-containing silicone resin. More 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 the curability. It is more preferably 0.08 to 2.2 ppm.

(Other ingredients)
In addition to the above-mentioned components, the thermosetting resin composition includes an inorganic filler, a coupling agent, a curing retarder, a thermosetting resin other than a silicone resin, an antioxidant, a mold release agent, a dispersant, an ion trapping agent, and the like. Various additives can be further contained.

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

In this specification, substances that have the effects of both pigments and inorganic fillers are, in principle, attributed to pigments. 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 shall belong to the inorganic filler. As the substance belonging to the inorganic filler, the substance excluding titanium oxide, zinc oxide, alumina, magnesium oxide, antimony oxide and zirconium oxide is given priority.

The central particle size 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, and 0. It is more preferably 5 to 75 μm. The content of the inorganic filler in the thermosetting resin composition is in the range of 4 to 85% by mass based on the total amount of the components that become solids after curing of the thermosetting resin composition from the viewpoint of further improving the moldability. It is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and even more preferably 20 to 80% by 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 even more preferably 30 to 90% by mass.

A coupling agent may be added to the thermosetting resin composition, if necessary. By containing a coupling agent, the interfacial adhesiveness between the silicone resin and an inorganic component such as a pigment or an inorganic filler can be improved. Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, and the like. As the silane coupling agent, known compounds such as epoxysilane-based, aminosilane-based, cationicsilane-based, vinylsilane-based, acrylicsilane-based, and mercaptosilane-based compounds can be generally used. The coupling agent may be a composite system of the above silane coupling agent. The amount of the coupling agent used is preferably 0.01 to 5% by mass based on the total amount of the thermosetting resin composition from the viewpoint of improving the curability. The pigment or the inorganic filler may be previously treated with the above-mentioned coupling agent.

A curing retarder may be added to the thermosetting resin composition from the viewpoint of improving storage stability, adjusting reactivity, and the like. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides.

Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, enyne compounds, maleic acid esters and the like. Examples of the organic phosphorus compound include triorganophosphins, diorganophosphins, organophosphons, triorganophosphytes and the like. 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, 1st to 3rd grade alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin-based compound include stannous halogenated dihydrate and stannous carboxylic acid. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

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

The amount of the curing retarder added is preferably in the range of 0.1 to 100 mol, 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 properties, a thermosetting resin other than the silicone resin can be added to the thermosetting resin composition within a range that does not adversely affect the properties. Examples of the thermosetting resin include, but are not limited to, epoxy resin, acrylic resin, cyanate resin, phenol resin, polyimide resin, polyamide-imide resin, and urethane resin. Of these, epoxy resin is preferable because it has excellent adhesiveness to metal parts and the like. The thermosetting resin is preferably colorless or relatively uncolored such as pale yellow.

The epoxy resin is not particularly limited, but for example, hexafluorobisphenol A type diglycidyl ether, hydrided bisphenol A type diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis (4-glycidyloxycyclohexyl) propane. , 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexendioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane)- Examples thereof include 1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate and diallyl monoglycidyl isocyanurate. From the viewpoint of heat resistance and ultraviolet resistance, an alicyclic epoxy resin is preferable, and from the same viewpoint, triglycidyl isocyanurate is more preferable.

When an epoxy resin is used, it is preferable to further contain a curing agent for the epoxy resin. From the viewpoint of heat-resistant discoloration, an acid anhydride-based curing agent is preferable as the curing agent, and examples of the acid anhydride-based curing agent include hexahydroanhydride phthalic acid, methylhexahydroanhydride phthalic acid, tetrahydroanhydride phthalic acid, and methyl hydride. Examples thereof include nagic 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 the thermosetting resin composition of the present embodiment is used as a light-reflecting material, the light reflectance after curing is preferably 80% or more at any of the wavelengths of 440 to 700 nm. When the light reflectance is 80% or more, the brightness 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 reflectance 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 ensuring a higher level of filling property in the mold. It is more preferably 60 to 100 cm. The spiral flow of the thermosetting resin composition can be measured, for example, by the method described in Examples described later.

When the thermosetting resin composition of the present embodiment is cured, the gel time (time until the composition loses fluidity and becomes a gel state) is set to, for example, 165 ° C. from the viewpoint of further improving moldability. It is preferably 10 to 60 seconds in the environment of. The gel time of the thermosetting resin composition can be measured, for example, by the method described in Examples described later.

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

(Kneading process)
The thermosetting resin composition can be prepared by uniformly dispersing and mixing 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 a device such as a mixing roll, an extruder, a kneader, a roll, an extruder, a rake, and a stirring mixer that combines rotation and revolution. The kneading type is not particularly limited, but melt kneading is preferable from the viewpoint of easy work, and kneading is preferably carried out at 15 to 30 ° C. from the viewpoint of simplifying the process. When heating is required, it may be in the temperature range of, for example, 30 to 100 ° C. When the temperature of melt-kneading is 30 ° C. or higher, various components can be melt-kneaded more sufficiently, and the dispersibility tends to be further improved. On the other hand, when melt-kneading is carried out at 100 ° C. or lower, it is possible to further suppress the increase in molecular weight of the resin composition and further suppress the curing of the resin composition 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 more, it is possible to further suppress the resin from seeping out from the mold when molding the substrate or the like, and when it is 40 minutes or less, it is easy to control the increase in the molecular weight of the resin composition, and the molding is performed. It is possible to further suppress the curing of the resin composition before.

The thermosetting resin composition subjected to the kneading step is preferably in a state where it can be subjected to the dry pulverization described later. Therefore, a step (cooling step) of cooling the thermosetting resin composition that has been kneaded may be provided before the pulverization step described later, if necessary.

(Crushing process)
In the pulverization step, for example, the thermosetting resin composition is dry pulverized. Dry pulverization can be performed using, for example, a pulverizer such as a high-speed stirring mill, a Henschel mixer, a power mill, a jet mill, or a roll granulator. These crushers can be used properly according to the desired powder particle size. In this way, a powdery thermosetting resin composition can be obtained.

In the method for producing a thermosetting resin composition according to the present embodiment, it is preferable to further include a third step of processing into a tablet shape after the second step. The tablet shape in the present specification means a solid state that retains a constant shape and has substantially no change in shape over time when left for about 30 minutes, for example. By being processed into a tablet shape, the handleability is further improved, and it is possible to improve the efficiency of transfer molding, compression molding and the like using the thermosetting resin composition. The shape of the tablet according to the present embodiment is not particularly limited and includes shapes such as columnar, prismatic, disk-shaped, and spherical, but columnar is preferable from the viewpoint of handleability.

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

The tablet-shaped thermosetting resin composition according to the present embodiment preferably has a type A durometer hardness of 50 or more, more preferably 55 or more, and even more preferably 60 or more. When the hardness is 50 or more, the tablet is less likely to be deformed and the handleability is better. Since the hardness of the tablet-like thermosetting resin composition is better, the upper limit 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 allowing the tablet-like thermosetting resin composition to stand at 25 ° C. for 3 minutes.

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

The method of coating the adherend with the filler is not particularly limited as long as it can come into contact with the tablet-like thermosetting resin composition. For example, a method of putting a filler in a container or a bag and coating the tablet-shaped thermosetting resin composition with the filler by vibration using a machine and a method of manually sprinkling the filler can be mentioned.

The thermosetting resin composition of the present embodiment is used in various applications such as an electrically insulating material, an optical semiconductor encapsulating material, an adhesive material, a coating material, and an epoxy resin molding material for transfer molding or compression molding, which require high heat resistance. It is useful. In particular, the thermosetting resin composition of the present embodiment is useful as a material for transfer molding. The thermosetting resin composition of the present embodiment is preferably white when used for light reflection applications.

The thermosetting resin composition of the present embodiment described above can be heat-cured to form a cured product. The conditions for thermosetting are not particularly limited, but for example, it can be cured by heating at a temperature of 170 to 200 ° C. for 60 to 300 seconds. Thermosetting may be performed as a part of the steps included in the molding method described later.

[Manufacturing method of substrate for mounting optical semiconductor devices]
The substrate for mounting an optical semiconductor device according to this embodiment has a recess formed by a bottom surface and a wall surface. The bottom surface of the recess is the optical semiconductor device mounting portion (optical semiconductor device mounting region), and the wall surface of the recess, that is, at least a part of the inner peripheral side surface of the recess is a molded product formed from the thermosetting resin composition of the present embodiment. It consists of. Further, the bottom surface of the recess is provided with a first connection terminal and a second connection terminal, and a molded body provided between them, and at least a part of the molded body has a thermosetting resin composition of the present embodiment. It is made of a molded body formed of an object.

FIG. 1 is a perspective view showing an embodiment of a substrate for mounting an optical semiconductor element. The substrate 110 for mounting an optical semiconductor element has 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). The metal wiring 105 provided with the insulating resin molded body 103'provided between the terminals) and the reflector 103 on which the Ni / Ag plating 104 was formed, and the insulating resin molded body 103'and the reflector 103 were formed. It has an optical semiconductor element mounting area (recess) 200. The bottom surface of the recess 200 is composed of a metal wiring 105 on which Ni / Ag plating 104 is formed and an insulating resin molded body 103', and the wall surface of the recess 200 is composed of a reflector 103. The reflector 103 and the insulating resin molded body 103'are molded bodies formed by using the thermosetting resin composition of the present embodiment.

The method for manufacturing the substrate for mounting the optical semiconductor element is not particularly limited, and for example, it can be manufactured by transfer molding or compression molding using a thermosetting resin composition. FIG. 2 is a schematic view showing an embodiment of a process of manufacturing a substrate for mounting an optical semiconductor device. In the substrate for mounting an optical semiconductor element, for example, a step of forming a metal wiring 105 by a known method such as punching from a metal foil and etching, and applying Ni / Ag plating 104 by electroplating ((a) in FIG. 2), and then A step of arranging the metal wiring 105 in a mold 151 having a predetermined shape, injecting a thermosetting resin composition from a resin injection port 150 of the mold 151, and performing transfer molding or compression molding under predetermined conditions (FIG. 2). It can be manufactured through the steps (b)) and the step of removing the mold 151 ((c) in FIG. 2).

In this way, the optical semiconductor device mounting region (recess) 200 surrounded by the reflector 103 made of the cured product of the thermosetting resin composition is formed on the optical semiconductor device mounting substrate. Further, the bottom surface of the recess 200 has an insulating property composed of a metal wiring 105 as a first connection terminal, a metal wiring 105 as a second connection terminal, and a cured product of a thermosetting resin composition provided between them. It is composed of 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 for 60 to 600 seconds, and an aftercure temperature of 120 ° C. to 180 ° C. 1 to 3 It is preferably time. 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. When the reflector is formed by compression molding, the molding temperature is 120 to 200 ° C. and 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 from the viewpoint of sufficient curing. It is preferable to do it in.

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

[Manufacturing method of optical semiconductor device]
The optical semiconductor device according to the present embodiment can be manufactured by mounting the semiconductor element on the substrate for mounting the optical semiconductor element obtained above. As a more specific example of the semiconductor device, the substrate for mounting the optical semiconductor element, the optical semiconductor element provided in the recess of the substrate for mounting the optical semiconductor element, and the seal that fills the recess and seals the optical semiconductor element. Examples thereof include an optical semiconductor device provided with a stop resin portion.

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 (recess) 200 of the optical semiconductor element mounting substrate 110, and is electrically connected to the metal wiring 105 by the bonding wire 102. To. 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 a substrate 110 for mounting an optical semiconductor element, an optical semiconductor element 100 provided at a predetermined position in a recess 200 of the substrate 110 for mounting an optical semiconductor element, and a recess 200. The metal wiring 105 in which the optical semiconductor device 100 and the Ni / Ag plating 104 are formed is provided with a sealing resin portion made of a transparent sealing resin 101 containing a phosphor 106 for filling and sealing the optical semiconductor element. And 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 an optical semiconductor device. In the optical semiconductor device shown in FIG. 6, the LED element 300 is arranged at a predetermined position on the lead 304 on which the reflector 303 is formed via the die bonding material 306, and the LED element 300 and the lead 304 are electrically connected by the bonding wire 301. The LED element 300 is connected and the LED element 300 is sealed by the transparent sealing resin 302 containing the phosphor 305.

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

Although the preferred embodiment of the present invention has been described above, the present invention is not limited thereto. For example, a molded product formed from the thermosetting resin composition according to the present embodiment can be used as a light-reflecting resin layer. As this embodiment, a copper-clad laminate, a substrate for mounting an optical semiconductor element, and an optical semiconductor element will be described.

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

FIG. 7 is a schematic cross-sectional view showing a preferred embodiment of the 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. There is. Here, the resin layer 402 is formed by using the thermosetting resin composition of the present embodiment described above. As the base material 401, the base material used for the copper-clad laminate can be used without particular limitation, and examples thereof include a resin laminate such as an epoxy resin laminate and a substrate for mounting an optical semiconductor element.

The copper-clad laminate 400 is produced, for example, by forming the thermosetting resin composition according to the present embodiment on the surface of the base material 401, stacking the copper foils 403, and heat-pressing and curing to form the resin layer 402. can do. The method of forming on the surface of the base material 401 is not limited, and examples thereof include a method of directly applying the substrate 401, a method of laminating a copper foil with a resin containing the thermosetting resin composition according to the present embodiment by pressing or laminating. The conditions for heating and pressurizing are not particularly limited, but for example, conditions of 130 to 180 ° C., 0.5 to 4 MPa, and 30 to 600 minutes are preferable.

Using the copper-clad laminate, it is possible to manufacture a printed wiring board for an optical member such as for mounting an optical semiconductor element. The copper-clad laminate 400 shown in FIG. 7 has a resin layer 402 and a copper foil 403 laminated on one side of the base material 401, whereas the copper-clad laminate has resin layers 402 on both sides of the base material 401. And copper foil 403 may be laminated respectively.

FIG. 8 is a schematic cross-sectional view showing an example of an optical semiconductor device manufactured by using a copper-clad laminate. As shown in FIG. 8, the optical semiconductor device 500 is a surface-mounted 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 adhered to the copper foil 403 via the adhesive layer 408, and is electrically connected to the copper foil 403 by the bonding wire 409.

Further, as another embodiment of the substrate for mounting an optical semiconductor device, an optical semiconductor provided with a resin layer formed between a plurality of conductor members (connection terminals) on a substrate by using the thermosetting resin composition described above. Examples include a substrate for mounting an element. Further, another embodiment of the optical semiconductor device is such that the optical semiconductor element is mounted on the above-mentioned optical semiconductor element mounting substrate.

FIG. 9 is a schematic cross-sectional view showing a preferred embodiment of the optical semiconductor device. As shown in FIG. 9, the optical semiconductor device 600 is a resin formed between a base material 601 and a plurality of conductor members 602 formed on the surface of the base material 601 and a plurality of conductor members (connection terminals) 602. A surface-mounted optical semiconductor in which an optical semiconductor element 610 is mounted on a substrate for mounting an optical semiconductor element including the layer 603 and a transparent sealing resin 604 is provided so that the optical semiconductor element 610 is sealed. It is a device. In the optical semiconductor device 600, the optical semiconductor element 610 is bonded to the conductor member 602 via the adhesive layer 608, and is electrically connected to the conductor member 602 by the bonding wire 609. The resin layer 603 is formed by using the thermosetting resin composition described above.

As the base material 601, the base material used for the substrate for mounting the optical semiconductor element can be used without particular limitation, and examples thereof include a resin laminated board such as an epoxy resin laminated board. The conductor member 602 functions as a connection terminal, and can be formed by a known method such as a method of photo-etching a copper foil. In the substrate for mounting an optical semiconductor element, a thermosetting resin composition is transfer-molded between a plurality of conductor members 602 on a base material 601 and heat-cured to form a resin layer 603 made of the thermosetting resin composition. It can be produced by the above. The heating conditions for heat-curing the layer made of the transfer-molded thermosetting resin composition are not particularly limited, but for example, heating is preferably performed under the conditions of 130 to 200 ° C. and 30 to 600 minutes.

After that, the resin component excessively adhered to the surface of the conductor member 602 is removed by buffing or the like to expose the circuit composed of the conductor member 602, and the substrate is used as a substrate for mounting an optical semiconductor element. Further, in order to ensure the adhesion between the resin layer 603 and the conductor member 602, the conductor member 602 may be subjected to a redox treatment, a CZ treatment (manufactured by MEC Co., Ltd.), or other roughening treatment.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above-mentioned embodiment. The present invention can be carried out in various embodiments different from the above embodiments without departing from the gist thereof.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Synthesis Example 1)
A solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of both-terminal dimethylchlorosilane-polydimethylsiloxane and 8.5 g of methylvinyldichlorosilane in 200 g of toluene was added dropwise to 1000 g of water so as not to generate heat and hydrolyzed. Then, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with potassium hydroxide, azeotropically dehydrated, and then a solvent such as toluene was distilled off to obtain a colorless liquid alkenyl group-containing silicone resin. The 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 added dropwise to 1000 g of water so as not to generate heat and hydrolyzed. Then, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with potassium hydroxide, azeotropically dehydrated, and then a solvent such as toluene was distilled off to obtain a colorless and transparent hydrosilyl group-containing silicone resin. The 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 both-terminal dimethylchlorosilane-polydimethylsiloxane and 40.3 g of methyldichlorosilane in toluene was added dropwise to 3000 g of water and hydrolyzed. Then, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with potassium hydroxide, azeotropically dehydrated, and then a solvent such as toluene was distilled off to synthesize a colorless and transparent hydrosilyl group-containing silicone resin. The 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-terminal dimethylchlorosilane-polydimethylsiloxane, and 31.6 g of dimethylchlorosilane in toluene was added dropwise to 3000 g of water for hydrolysis. Then, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with potassium hydroxide, azeotropically dehydrated, and then a solvent such as toluene was distilled off to synthesize a colorless and transparent hydrosilyl group-containing silicone resin. The 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. Then, toluene was distilled off under reduced pressure to obtain an alkenyl group-containing silicone resin. The Mw of the obtained alkenyl group-containing silicone resin was 2400.

[Preparation of thermosetting resin composition for light reflection]
(Examples 1 to 5)
<First step: Preparation of prepolymer>
Prepolymers 1 to 5 were obtained by blending each component according to the blending ratio (parts by mass) shown in Table 1 and sufficiently kneading and dispersing at room temperature with a raker. The Mw of the obtained prepolymers 1 to 5 is shown in Table 1.

<Second step: Preparation of thermosetting resin composition>
Each component was blended according to the blending ratio (parts by mass) shown in Table 2 and sufficiently kneaded and dispersed at room temperature with a raker to obtain a powdery thermosetting white resin composition.

(Comparative Examples 1 to 5)
According to the blending ratio (parts by mass) shown in Table 3, each component is blended at once without prepolymerization, and the mixture is sufficiently kneaded and dispersed at room temperature by a raker to obtain a powdery thermosetting white resin composition. Got

The details of * 1 to * 12 in Table 1, Table 2 and Table 3 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 (manufactured by Momentive Performance Materials, trade name "TSF484")
* 4: Silicon compound having an alkenyl group (manufactured by Momentive Performance Materials, trade name "XC96-C0214")
* 5: Silicon compound having an alkenyl group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-1003")
* 6: Silicone resin containing an alkenyl group (Synthesis Example 5)
* 7: Silicone resin containing an alkenyl group (Synthesis Example 1)
* 8: Hydrosilyl group-containing silicone resin (Synthesis Example 2)
* 9: Titanium oxide (manufactured by 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 (manufactured by Wako Pure Chemical Industries, Ltd., platinum 1.7% by mass)
* 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 Admatex Co., Ltd., trade name "SO-25R", center particle size 1 μm)

The measurement method of each characteristic in the above synthesis example, example and comparative example is as follows.

(Measurement of weight average molecular weight (Mw))
Using Mw as a GPC measuring device, pump "L-6200 type" (manufactured by Hitachi, Ltd., product name), columns "TSKgel-G5000HXL" and "TSKgel-G2000HXL" (manufactured by Tosoh Corporation, product name) and detector " It was measured using "L-3300RI type" (manufactured by Hitachi, Ltd., trade name). The measurement conditions were tetrahydrofuran as the eluent, a temperature of 30 ° C., and a flow rate of 1.0 mL / min.

(Measurement of formability)
As a mold for measuring moldability, a mold composed of an upper mold and a lower mold having a recess for molding a disk-shaped molded product having a diameter of 20 mm and a thickness of 2 mm and a resin injection port was used. .. Using the thermosetting resin compositions 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 to mold a test piece. By visually observing the test piece, the presence or absence of an unfilled portion was confirmed. The evaluation result was "A" when no unfilled portion was found and "B" when an unfilled portion was found.

(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 onto a hot plate at 165 ° C. until the fluidity was lost and the gel state was obtained. Time was measured.

(Measurement of spiral flow)
According to 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 measuring die. The flow distance (cm) of the resin composition at that time was measured.

(Measurement of light reflectance)
The thermosetting resin compositions prepared in each Example and each Comparative Example 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 to prepare a plate-shaped test piece having a thickness of 3 mm. The light reflectance at a wavelength of 46 nm was measured for the prepared test piece using an integrating sphere spectrophotometer CM600d (manufactured 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 the silicone resin is not prepolymerized. Further, in the examples, the gelation time is longer than that in the comparative example, and the value of the spiral flow is large. From these facts, the thermosetting resin composition according to the present invention can reduce the generation of unfilled portions due to rapid curing during transfer molding.

100 ... Optical semiconductor device, 101 ... Transparent sealing resin, 102 ... Bonding wire, 103 ... Reflector, 103'... Insulating resin molded body, 104 ... Ni / Ag plating, 105 ... Metal wiring, 106 ... Fluorescent material, 107 ... Solder bump, 110 ... Optical semiconductor device mounting substrate, 150 ... Resin injection port, 151 ... Mold, 200 ... Optical semiconductor device 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 ... base material, 402 ... resin layer, 403 ... copper foil, 404 ... sealing resin, 408 ... adhesive layer, 409 ... Bonding wire, 410 ... Optical semiconductor device, 500, 600 ... Optical semiconductor device, 601 ... Base material, 602 ... Conductor member, 603 ... Resin layer, 604 ... Sealing resin, 608 ... Adhesive layer, 609 ... Bonding wire, 610 … Optical semiconductor device.

Claims (9)

The 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.
Equipped with
In the second step, the mixing ratio of the prepolymer, the total amount 100 parts by weight of the hydrosilyl group-containing silicone resin and the alkenyl group-containing silicone resin, Ru 10-80 parts by der, thermosetting A method for producing a resin composition. The method of claim 1, wherein the prepolymer has a weight average molecular weight of 1000-90000. In the first step, the hydrosilyl group-containing silicone resin is mixed so that the molar ratio of the hydrosilyl group is 10 to 60 mol with respect to 1 mol of the alkenyl group of the silicon compound, according to claim 1 or 2. The method described in. The method according to any one of claims 1 to 3 , wherein the pigment comprises 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 according to any one of claims 1 to 4 , further comprising a third step of processing the thermosetting resin composition into a tablet shape. A method for manufacturing a substrate for mounting an optical semiconductor device having a recess composed of a bottom surface and a wall surface.
The present invention comprises 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 5. , A method for manufacturing a substrate for mounting an optical semiconductor element. An optical semiconductor device including 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. It is a method of manufacturing a mounting board.
A light comprising a step of forming at least a part of the molded product by transfer molding or compression molding using the thermosetting resin composition obtained by the method according to any one of claims 1 to 5. A method for manufacturing a substrate for mounting a semiconductor element. A method for manufacturing an optical semiconductor device including 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 the optical semiconductor element obtained by the method according to claim 6 or 7. Prepolymer is a reaction product of a silicon compound having a hydrosilyl group-containing silicone resin and an alkenyl group, a hydrosilyl group-containing silicone resin, seen containing an alkenyl group-containing silicone resin and pigment,
A thermosetting resin composition in which the content of the prepolymer 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.

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