JP6322929B2 - Thermosetting resin composition for light reflection, substrate for mounting optical semiconductor element, method for manufacturing the same, and optical semiconductor device - Google Patents

Description

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

  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 portable liquid crystal backlight, an in-vehicle application, etc. due to the advantages of high energy efficiency and long life. This is applied to various uses and its demand is expanding.

  Along with this, the brightness of LED devices has been increasing, and the rise in junction temperature due to an increase in the amount of heat generated by the element, or the deterioration of element materials due to a direct increase in light energy, has been regarded as a problem. Development of a device material having resistance to the problem has been an issue.

  As a technique for preventing the problem of luminance reduction caused by heat or light, Patent Document 1 proposes a substrate for mounting an optical semiconductor element in which a reflector having a high light reflectance is provided at a portion where the optical semiconductor element is mounted. ing. Patent Documents 1 and 2 disclose that a reflector is formed by transfer molding, and a light-reflective thermosetting resin composition containing an epoxy resin, a curing agent, a curing catalyst, and a white pigment is used as the material. Proposed.

JP 2006-140207 A JP 2013-155344 A

  In manufacturing an LED package, a high-temperature process such as connection between a substrate for mounting an optical semiconductor element and the optical semiconductor element, resin sealing of the optical semiconductor element, and solder reflow during mounting on the substrate is performed. Further, when the LED package is used, the resin material may be hydrolyzed due to the influence of humidity in the atmosphere and the influence of heat generated from the LED element. In the case of an optical semiconductor element mounting substrate manufactured using a conventional thermosetting resin composition for light reflection, it is difficult to ensure the initial optical characteristics of the LED package due to atmospheric humidity or heat generated during operation. Sometimes.

  Generally, an epoxy resin is used for the thermosetting resin composition for light reflection used for transfer molding. In order for an optical semiconductor device to perform a stable operation in a higher temperature and higher humidity environment, it is required that the epoxy resin constituting them be difficult to discolor due to heat or humidity.

  The present invention has been made in view of the above circumstances, has a sufficient light reflectivity, and can form a molded article excellent in moisture resistance and heat-resistant colorability. It is an object of the present invention to provide an optical semiconductor element mounting substrate, a method for manufacturing the same, and an optical semiconductor device.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, it is possible to form a molded article with high light reflectance by transfer molding by blending a specific epoxy compound with a thermosetting resin composition. In addition, the present inventors have found that it has resistance to atmospheric humidity and can lower the light reflectivity of the molded product after heat treatment at high temperature, compared to the prior art.

The present invention includes an epoxy resin, a curing catalyst, and a white pigment, and the epoxy resin contains a fluorinated epoxy resin represented by the following general formula (1) and a polyorganosiloxane having an epoxy group. The present invention relates to a thermosetting resin composition. In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents a number from 0 to 40.

  The polyorganosiloxane having an epoxy group is preferably a condensate of a silane compound having an epoxy group and a silane compound having no epoxy group.

  The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 150 to 1000 g / eq. The number average molecular weight of the polyorganosiloxane having an epoxy group is preferably 300 to 5,000.

  The thermosetting resin composition for light reflection may further contain a curing agent.

  The white pigment preferably contains at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zinc oxide, zirconium oxide and inorganic hollow particles. The center particle diameter of the white pigment is preferably 0.1 to 50 μm. The content of the white pigment is preferably 10 to 85% by volume based on the total amount of the thermosetting resin composition. When the white pigment satisfies these conditions, the effect of the present invention is more remarkably exhibited.

  In another aspect, the present invention relates to an optical semiconductor element mounting substrate comprising a cured product of the light reflecting thermosetting resin composition. The substrate for mounting an optical semiconductor element may have a recess composed of a bottom surface and a wall surface, and the bottom surface of the recess may be a mounting portion for the optical semiconductor element. In this case, at least a part of the wall surface of the recess is a cured product of the thermosetting resin composition for light reflection. The optical semiconductor element mounting substrate is provided between the substrate, the first connection terminal and the second connection terminal provided on the substrate, and the first connection terminal and the second connection terminal. And a cured product of the thermosetting resin composition for light reflection.

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

  In still another aspect, the present invention relates to a method for manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface. The manufacturing method according to the present invention includes a step of forming at least a part of the wall surface of the recess by transfer molding the thermosetting resin composition for light reflection.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition for light reflection which can form the molded object which has sufficient light reflectivity and was excellent in moisture resistance and heat-resistant coloring property can be provided. That is, according to the present invention, a cured product having a high light reflectance in the wavelength region from visible light to near-ultraviolet light is obtained, and at the time of manufacturing an optical semiconductor device such as an LED package, or when used in a high temperature environment. A thermosetting resin composition for light reflection capable of obtaining a cured product with less discoloration can be provided. In addition, by using such a resin composition, it is possible to manufacture an optical semiconductor element mounting substrate and an optical semiconductor device having excellent optical characteristics and high reliability.

It is a perspective view which shows suitable 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 suitable 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.

[Thermosetting resin composition for light reflection]
The light-reflective thermosetting resin composition of the present embodiment includes (A) an epoxy resin, (B) a curing catalyst, and (C) a white pigment. The thermosetting resin composition is characterized by containing, as (A) an epoxy resin, a specific fluorinated epoxy resin described later and a polyorganosiloxane having an epoxy group. Hereinafter, each component will be described.

((A) component: epoxy resin)
The fluorinated epoxy resin contained in the light-reflective thermosetting resin composition is an epoxy resin represented by the following general formula (1) (hereinafter referred to as “component (A1)” in some cases).

In the formula, each of R ¹ , R ² , R ³ and R ⁴ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and is a hydrogen atom, a methyl group, an ethyl group or a halogen atom. Is preferred.

  In formula, n is the range of 0-40, Preferably it is the range of 0-20. When n exceeds 40, the molecular weight increases, so the viscosity and softening temperature increase, and the handleability tends to decrease. The value of n can be controlled by the molar ratio of the epihalohydrin to the bisphenol compound at the time of producing the epoxy resin, and n is an average value. The “component (A1)” preferably contains 10 mol% or more of a component having n = 0. When the component where n is 0 is 10 mol% or more, the viscosity and the softening temperature are easily adjusted, and the handling becomes easy. The average value of n is more preferably 0 to 10, particularly preferably 0 to 5.

  The epoxy equivalent of the fluorinated epoxy resin represented by the general formula (1) is preferably 224 to 2000 g / eq, and more preferably 224 to 1000 g / eq. When the epoxy equivalent is 2000 g / eq or less, the handleability tends to be improved.

  The fluorinated epoxy resin represented by the general formula (1) is obtained by performing an addition / ring-closure reaction between a bisphenol compound represented by the following general formula (2) and an epihalohydrin in the presence of a base such as an alkali metal hydroxide. Can be obtained.

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and may be a hydrogen atom, a methyl group, an ethyl group or a halogen atom. preferable.

  Examples of the fluorinated epoxy resin represented by the general formula (1) include an epoxy resin obtained from 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,2-bis (4-hydroxy-3-methyl). Epoxy resin obtained from phenyl) hexafluoropropane, epoxy resin obtained from 2,2-bis (3-ethyl-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3,5-dimethyl) Epoxy resin obtained from phenyl) hexafluoropropane, epoxy resin obtained from 2,2-bis (3-bromo-4-hydroxyphenyl) hexafluoropropane, and 2,2-bis (3,5-dibromo-4) An epoxy resin obtained from -hydroxyphenyl) hexafluoropropane can be mentioned.

Examples of the bisphenol compound represented by the general formula (2) used as a raw material for producing such an epoxy resin include 2,2-bis (4-hydroxyphenyl) hexafluoropropane and 2,2-bis (4-hydroxy-3- Methylphenyl) hexafluoropropane, 2,2-bis (3-ethyl-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, 2,2 -Bis (3-fluoro-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-bromo-4-hydroxyphenyl) hexafluoropropane and 2,2-bis (3,5-dibromo-4-hydroxy) Phenyl) hexafluoropropane. Among these, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, in which R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, is particularly preferable from the viewpoint of easy availability of raw materials.

  The light transmittance (hereinafter sometimes referred to as “light transmittance (50)”) of a solution obtained by dissolving the bisphenol compound represented by the general formula (2) in a ketone solvent so as to have a concentration of 50% by mass is 80% or more. When it is, the hue of the thermosetting resin composition for light reflections obtained will become good. The improvement in hue means that the optical reflectance of the obtained light-reflective thermosetting resin composition is increased, and the optical output of an optical semiconductor device using the same can be improved.

  More specifically, the light transmittance (50) is obtained by dissolving the bisphenol compound solution in a quartz cell having an optical path length of 1 cm after dissolving in a ketone solvent so that the concentration of the bisphenol compound is 50% by mass. , By measuring the light transmittance at a wavelength of 400 nm using a spectrophotometer. However, this concentration does not need to be 50% by mass with high accuracy, and may be a concentration range of 49.5 to 50.5% by mass. As the ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or a mixed solvent thereof can be used.

  The light transmittance (50) of the bisphenol compound is preferably as high as possible, and particularly preferably 85% or more. Although there is no restriction | limiting in particular about the upper limit of light transmittance (50), Usually, it is 95% or less.

  As a method for improving the hue so that the light transmittance (50) of the bisphenol compound represented by the general formula (2) is 80% or more, a mixed solvent of a water-soluble organic solvent and water (preferably pure water) is used. Among them, there are a method of recrystallizing to remove impurities to improve the hue, a method of decolorizing using a reducing agent or an adsorbent, and the like.

  The organic solvent that can be used for recrystallization of the bisphenol compound is not particularly limited as long as it is compatible with water. For example, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, and water-soluble alcohols Is mentioned. Examples of water-soluble alcohols include monohydric alcohols such as methanol, ethanol, n-propanol, and isopropanol, divalent alcohols such as ethylene glycol, diethylene glycol, and triethylene glycol, and methyl cellosolve and ethyl cellosolve. And cellosolves such as butyl cellosolve. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

  Among these organic solvents, water-soluble alcohols are particularly preferable in that the purity of the bisphenol compound is effectively improved. The mixing ratio of the organic solvent used for recrystallization and the mixed solvent of water is 5 to 5. 50% by mass and 50 to 95% by mass of water are preferable.

  Recrystallization of the bisphenol compound can be performed by a usual method. For example, 1 to 50 parts by mass of a mixed solvent of an organic solvent and pure water is added to 1 part by mass of the bisphenol compound, and the vicinity of the boiling point of the mixed solvent The temperature can be raised to a uniform solution, and then cooled to near room temperature to precipitate bisphenol compound crystals again.

  A method of decolorizing a bisphenol compound using a reducing agent or an adsorbent is usually to contact a reducing agent or an adsorbent with a solution in which the bisphenol compound is dissolved in a solvent, and reduce the quinones with the reducing agent, or the adsorbent. It can be performed by removing impurities by adsorption.

  Examples of reducing agents include N, N-diethylhydroxylamine, hydrazine hydrate, ascorbic acid, sodium nitrite, sodium borohydride, lithium aluminum hydride, polymethylhydrosiloxane, stannic chloride, trichloride One or more reducing agents capable of reducing quinones such as titanium are included.

  Examples of the adsorbent include one or more commonly used adsorbents such as activated clay, activated carbon, magnesium oxide, silica gel, alumina, silica alumina, and the like.

  The treatment with the reducing agent and the treatment with the adsorbent may be used together. In that case, the treatment with the adsorbent may be performed after the treatment with the reducing agent, and conversely, after the treatment with the adsorbent, You may perform the process by a reducing agent.

  When performing a decoloring process with a reducing agent or an adsorbent, an epichlorohydrin and an alcohol solvent are usually used for the bisphenol compound, and the bisphenol compound is usually dissolved in a concentration of about 10 to 40% by mass and used for the decoloring process. It is preferable not to isolate the bisphenol compound after the decolorization treatment, and then to perform an epoxidation reaction.

  When performing the decoloring process by a reducing agent, the above-mentioned reducing agent is added to the above bisphenol compound solution about 0.1-5 mass% with respect to a bisphenol compound, and it is 0.2- The quinones are reduced and removed by stirring for about 3 hours.

  In the case of performing a decolorization treatment with an adsorbent, the bisphenol compound solution is passed through a column filled with the adsorbent described above, or the adsorbent is added to the bisphenol compound solution with stirring and mixed, and then solid-liquid separation is performed.

  By performing such decolorization treatment or the above-described recrystallization, a bisphenol compound having a light transmittance (50) of 80% or more can be obtained.

  The aforementioned decolorization treatment can also be performed on the produced epoxy resin. In this case, if the same decolorization treatment as that for the above-mentioned bisphenol compound is performed on a solution in which the epoxy resin can be dissolved in one or two or more organic solvents at a concentration of about 10 to 50% by mass. Good. By performing such decoloring treatment, or by producing an epoxy resin using a bisphenol compound having a light transmittance (50) of 80% or more by the above-mentioned recrystallization or decolorization treatment, light transmittance (50) 80% or more of the (A1) component epoxy resin can be obtained.

  When the light-reflective thermosetting resin composition contains a curing agent described later, the component (A1) is preferably compatible with the curing agent. The term “compatible with the curing agent” for the epoxy resin means that the epoxy resin has an affinity with other curing agents and exists as a uniform solution or mixture. More specifically, for example, a mixture obtained by mixing an epoxy resin and a curing agent at a mass ratio of 1/1, completely dissolving these components at 120 ° C., and subsequently stirring the mixture, When a part of the mixed liquid is taken out and visually observed after standing for a minute, it means a state that can be confirmed as a transparent liquid with no separation between components. In this specification, such a state is referred to as “compatible with each other”, and a case where components are separated and become an opaque liquid is referred to as “insoluble with each other”. The combination of epoxy resin and curing agent that are compatible with each other but require a long time to dissolve requires heating over a long period of time, that is, more heat energy. It is disadvantageous in terms of sex or cost. Therefore, a combination that is compatible in a short time is preferable.

  Furthermore, in the above mixing operation, a gel or the like that is a cured reaction product of an epoxy resin and a curing agent may be precipitated. It is preferable to select the mixing conditions. In addition, if a material having a high viscosity is selected, bubbles are involved by stirring, and the resulting mixture may be observed to be cloudy in appearance due to minute bubbles. In that case, it is preferable to determine the transparency of the mixture after removing bubbles by a known vacuum degassing method. Note that “white turbidity” indicates that there is no scattering of electromagnetic waves in the visible light region. More specifically, it indicates that there are no fine particles or minute bubbles having scattering centers that cause the Rayleigh scattering, Mie scattering, and diffraction scattering phenomena of light.

  The fluorinated epoxy resin has a bond with high binding energy, and the fluorinated main skeleton exhibits hydrophobicity, which reduces the surface free energy of the cured molded product surface of the thermosetting resin composition for light reflection. Have From such properties, it becomes possible to suppress the resin composition from sticking to the molding die during transfer molding. And by combining such a compound with (B) a curing catalyst and (C) a white pigment, it is sufficient to perform a molding process using a mold at a high temperature while suppressing coloring due to oxidative degradation in a high temperature environment. Even in the case of producing a molded article having a good light reflectance, it is possible to ensure sufficient releasability from the molding die at the time of molding the mold, and the high light reflectance, heat resistance coloring property and molding processability. Everything can be highly satisfied.

  The melting point or softening point of the fluorinated epoxy resin is preferably 0 to 150 ° C, more preferably 30 to 100 ° C, and still more preferably 30 to 80 ° C. When the melting point or softening point of the fluorinated epoxy resin is 0 ° C. or higher, the dispersibility of the white pigment in the thermosetting resin composition for light reflection tends to be improved, and molding is performed using a mold like transfer molding. In this case, resin burrs are less likely to occur. When the resin burrs are generated, they remain as contaminants on the optical semiconductor mounting substrate, and when the optical semiconductor element is mounted in a subsequent process, sufficient connection strength cannot be obtained, which may cause defects. On the other hand, when the melting point or softening point of the above compound is 150 ° C. or lower, the melt viscosity of the thermosetting resin composition hardly increases, and the processing characteristics when melted and molded into a fluid state tend to be improved.

  The melt viscosity at 150 ° C. of the fluorinated epoxy resin is preferably 1.0 to 1000 mPa · s, more preferably 10 to 1000 mPa · s, and still more preferably 100 to 1000 mPa · s. When the melt viscosity is 1.0 mPa · s or more, the dispersibility of the white pigment in the light-reflective thermosetting resin composition tends to be improved, and when molding using a mold as in transfer molding. Resin burrs are less likely to occur. On the other hand, when the melt viscosity is 1000 mPa · s or less, the melt viscosity of the thermosetting resin composition hardly increases, and the processing characteristics when melted and molded into a fluid state tend to be improved.

  In the present specification, “melt viscosity at 150 ° C.”, “softening point (melting point)” and “number average molecular weight (Mn)” are determined by the following measuring methods, respectively. “Melt viscosity at 150 ° C.” is available from Research Equipment (London) LTD. It is measured using a manufactured ICI cone plate viscometer. The “softening point (melting point)” is obtained by heating the compound on a hot plate and visually confirming the change in properties. “Number average molecular weight (Mn)” refers to a value measured using a standard polystyrene calibration curve in accordance with a gel permeation chromatography (GPC) method. More specifically, a pump (Hitachi, Ltd.) is used as a GPC measuring device. Manufactured by L-6200 type), column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, trade name) and detector (manufactured by Hitachi, Ltd., L-3300RI type) as an eluent. Tetrahydrofuran is used, and measurement is performed under the conditions of a temperature of 30 ° C. and a flow rate of 1.0 mL / min.

  As the fluorinated epoxy resin represented by the general formula (1), commercially available resins can be used. For example, trade names “YL7702”, “YL7763-65” and “YL7763-65” manufactured by Mitsubishi Chemical Corporation can be used. YL7763-65 ".

  When the thermosetting resin composition for light reflection contains the component (A1), a polyorganosiloxane having an epoxy group (hereinafter sometimes referred to as “component (A2)”), a curing catalyst and a white pigment are uniformly mixed. It becomes possible to dissolve and disperse and mix.

  In general, it is known that polyorganosiloxane has low compatibility with hydrocarbon-based materials such as epoxy resins. Usually, when using an epoxy resin having a polyorganosiloxane skeleton, it is necessary to have compatibility with components other than the epoxy resin in order to improve the processability of the light-reflective thermosetting resin composition. In order to impart compatibility, an epoxy resin obtained by modifying a high molecular weight hydrocarbon component into polyorganosiloxane is used. However, the polyorganosiloxane-containing epoxy resin containing a large amount of hydrocarbon components may not have sufficient heat resistance and moisture resistance.

  On the other hand, the polyorganosiloxane having an epoxy group according to the present embodiment has a bond with high binding energy, the organosiloxane skeleton exhibits hydrophobicity, and improves the moisture resistance after the resin composition is thermally cured. Have properties. By using such a compound in combination with the fluorinated epoxy resin, the molded product formed from the light-reflective thermosetting resin composition suppresses coloring due to oxidative degradation under a high-temperature environment, while maintaining moisture resistance. It can improve and can fully satisfy all of high light reflectance, heat-resistant coloring property, and moldability.

  As the polyorganosiloxane having an epoxy group, a condensate of a silane compound having an epoxy group and a silane compound having no epoxy group can be used.

As a silane compound which has an epoxy group, the compound shown by following General formula (3) is mentioned, for example.
(R ⁵ ) _g Si (OX ¹ ) _4-g (3)

In Formula (3), R ⁵ represents an organic group having 2 to 20 carbon atoms having an epoxy group, X ¹ represents an alkyl group having 1 to 10 carbon atoms, g represents an integer of 1 or 2, When g is 2, two R ⁵ may be the same or different.

  Although it does not specifically limit as a C2-C20 organic group which has an epoxy group, For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycid Examples include a xylethyl group, a 3-glycidoxypropyl group, a 4-glycidoxybutyl group, and a group represented by the following formula (3a).

  In formula (3a), p represents an integer of 1 to 10, is preferably an integer of 2 to 6, and is more preferably an integer of 2 to 4. As the group represented by the formula (3a), a 2- (3,4-epoxycyclohexyl) ethyl group or a 3- (3,4-epoxycyclohexyl) propyl group can be suitably used.

X ¹ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. g is preferably 1.

As the silane compound having no epoxy group, for example, a compound represented by the following general formula (4) can be used.
(R ⁶ ) _h Si (OX ² ) _4-h (4)

In Formula (4), R ⁶ represents an organic group having 1 to 20 carbon atoms that does not have an epoxy group, X ² represents each independently an alkyl group having 1 to 6 carbon atoms, and h is an integer of 1 or 2. When h is 2, two R ⁶ may be the same or different.

  Although it does not specifically limit as a C1-C20 organic group which does not have an epoxy group, For example, alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group; Alkenyl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group; chloromethyl group, 3-chloro group, aryl group, butenyl group, pentenyl group, hexenyl group Examples thereof include substituted alkyl groups such as propyl group, 3,3,3-trifluoropropyl group, and nonafluorobutylethyl group. As a C1-C20 organic group which does not have an epoxy group, an alkyl group or an aryl group is preferable, and a methyl group or a phenyl group is more preferable.

X ² is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. h is preferably 1.

  The polyorganosiloxane having an epoxy group is obtained by hydrolytic condensation of a compound represented by the general formula (3) and a silane compound containing the compound represented by the general formula (4) in the presence of water and a basic catalyst. Can be obtained at The compound represented by the general formula (3) and the compound represented by the general formula (4) may be used singly or in combination of two or more.

Along with the compound represented by the general formula (3) and the compound represented by the general formula (4), hydrolysis condensation may be performed using a compound represented by the following general formula (5).
(R ⁷ ) ₃ SiOX ³ (5)

In formula (5), R < ⁷ > shows the C1-C20 organic group which does not have an epoxy group each independently, The group similar to R < ⁶ > is illustrated. X ³ represents an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

  Examples of the compound represented by the general formula (5) include monoalkoxysilane compounds such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane.

  The lower limit of the epoxy equivalent of the polyorganosiloxane having an epoxy group as the component (A2) is preferably 150 g / eq or more, more preferably 200 g / eq or more, still more preferably 320 g / eq or more, and particularly preferably 350 g / eq or more. preferable. When the epoxy equivalent is 150 g / eq or more, the mass ratio of the siloxane unit contained in the component (A2) increases, and the heat resistance and the color resistance tend to be improved. On the other hand, the upper limit of the epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 1000 g / eq or less, more preferably 500 g / eq or less, still more preferably 450 g / eq or less, and particularly preferably 400 g / eq or less. When the epoxy equivalent is 1000 g / eq or less, compatibility is improved when preparing a thermosetting resin composition for light reflection by mixing with components such as component (A1) and a curing catalyst, and melt molding. The processing characteristics tend to be excellent.

  The number average molecular weight of the component (A2) is preferably 700 to 5000, more preferably 900 to 4000, and still more preferably 1000 to 3000. When the number average molecular weight is 700 or more, the mass ratio of the siloxane unit in the component (A2) increases, and the heat resistance and coloration resistance tend to be improved. On the other hand, when the number average molecular weight is 5000 or less, the melt viscosity of the thermosetting resin composition can be reduced, and the processing characteristics during melt molding tend to be excellent.

  The component (A2) preferably has a melting point or softening point of 0 to 150 ° C, more preferably 20 to 120 ° C, and still more preferably 40 to 100 ° C. When the melting point or softening point of the component (A2) is 0 ° C. or higher, the dispersibility of the white pigment in the thermosetting resin composition for light reflection tends to be improved, and molding is performed using a mold as in transfer molding. In this case, resin burrs are less likely to occur. On the other hand, when the melting point or softening point of the component (A2) is 150 ° C. or less, the melt viscosity of the thermosetting resin composition is difficult to increase, and the processing characteristics when melted and molded into a fluid state tend to be improved. is there.

  The component (A2) preferably has a melt viscosity at 150 ° C. of 1.0 to 1000 mPa · s. When the melt viscosity of the component (A2) is 1.0 mPa · s or more, the dispersibility of the white pigment in the thermosetting resin composition for light reflection tends to be improved, and a mold is used as in transfer molding. Resin burrs are less likely to occur when molding. On the other hand, if the melt viscosity is 1000 mPa · s or less, the melt viscosity of the thermosetting resin composition becomes difficult, and the processing characteristics when melted and molded into a fluid state tend to be improved.

  Content of the (A1) component and the (A2) component in the thermosetting resin composition for light reflection is 0.1-20 mass% on the basis of the total amount of components that become a solid content after curing of the thermosetting resin composition. It is preferable that it is 3 to 20% by mass.

  The content of the component (A2) in the light-reflective thermosetting resin composition is preferably 1 to 1000 parts by mass, and 10 to 800 parts by mass with respect to 100 parts by mass of the component (A1). Is more preferable, and it is still more preferable that it is 20-500 mass parts. When the component (A2) is 1000 parts by mass or less, it is easy to obtain compatibility or dispersibility with a curing catalyst, a white pigment and the like, and when it is 1 part by mass or more, improvement in moisture resistance based on the polyorganosiloxane skeleton. It becomes easy to demonstrate the effect.

  The thermosetting resin composition for light reflection can further contain an epoxy resin (hereinafter referred to as “component (A3)”) other than the component (A1) and the component (A2) as the epoxy resin (A). In this case, from the viewpoint of suppressing a decrease in optical reflectance under a high temperature environment, the content of the component (A2) is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the component (A1). More preferably, it is -180 mass parts, and it is still more preferable that it is 20-150 mass parts. When the component (A2) is 200 parts by mass or less, compatibility or dispersibility with a curing catalyst, a white pigment or the like is easily obtained, and when it is 1 part by mass or more, improvement in moisture resistance based on the polyorganosiloxane skeleton. It becomes easy to demonstrate the effect.

  As the component (A3), a generally known epoxy resin molding material can be used. For example, a novolac epoxy resin such as a phenol novolac epoxy resin or an orthocresol novolac epoxy resin; a bisphenol A epoxy resin, Diglycidyl ethers such as bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, alkyl-substituted bisphenol-type epoxy resin; glycidylamine-type epoxy resin obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; And linear aliphatic epoxy resins obtained by oxidation with a peracid such as peracetic acid; and alicyclic epoxy resins. These can be used alone or in combination of two or more.

  As the component (A3), a relatively uncolored epoxy resin such as colorless or light yellow is preferable. Specific examples of such an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate and triglycidyl isocyanurate.

((B) component: curing catalyst)
Examples of the curing catalyst include tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, tri-2,4,6-dimethylaminomethylphenol; 2-ethyl-4 Imidazoles such as methylimidazole and 2-methylimidazole; triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate And phosphorus compounds such as tetra-n-butylphosphonium-tetraphenylborate; quaternary ammonium salts; and organometallic salts; and derivatives thereof. These may be used alone or in combination of two or more. Among these curing catalysts, tertiary amines, imidazoles or phosphorus compounds are preferably used.

  A thermal cationic polymerization initiator (thermal acid generator) can also be used as the curing catalyst. As the thermal cationic polymerization initiator, those having an anion component of hexafluorophosphate ion, tetrafluoroborate ion, tetrafluoroantimonate ion or tetra (hexafluorophenyl) borate ion can be used. It is preferable to use an onium salt containing a hexafluorophosphate ion as an anion component. Examples of the cation component include diazonium salts, sulfonium salts, iodonium salts, selenium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. From the viewpoint of heat reactivity, an aromatic sulfonium salt is preferable as the thermal cationic polymerization initiator. For example, dimethyl-p-acetoxyphenylsulfonium hexafluoroantimonate can be used.

  The content of the curing catalyst in the light-reflective thermosetting resin composition is preferably 0.01 to 8.0% by mass based on the total amount of (A) the epoxy resin, and is preferably 0.1 to 3.0. It is more preferable that it is mass%, and it is still more preferable that it is 0.3-2.0 mass%. When the content of the curing catalyst is 0.01% by mass or more, a curing accelerating effect is easily obtained, and when it is 8.0% by mass or less, the obtained cured product (molded body or the like) is difficult to be discolored. .

(Curing agent)
The thermosetting resin composition for light reflection may use a curing agent together with a curing catalyst. Any curing agent may be used as long as it can react with the epoxy resin (A) to obtain a cured product, and specific examples thereof include acid anhydride curing agents, isocyanuric acid derivatives, and phenolic curing agents. From the viewpoint of moldability and the mechanical properties of the cured product, the curing agent preferably has a molecular weight of about 100 to 400. The curing agent is preferably a relatively uncolored one such as colorless or light yellow.

  Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, and glutaric anhydride. Dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride. These may be used alone or in combination of two or more.

  Examples of the isocyanuric acid derivatives include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3- Carboxypropyl) isocyanurate and 1,3-bis (2-carboxyethyl) isocyanurate. These may be used alone or in combination of two or more.

  Examples of phenolic curing agents include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene. , Formaldehyde, benzaldehyde, salicylaldehyde, and other aldehydes obtained by condensation or cocondensation in the presence of an acidic catalyst; novolak-type phenol resins; phenols and / or naphthols; Phenol-aralkyl resins synthesized from aralkyl-type phenol resins such as biphenylene-type phenol-aralkyl resins and naphthol-aralkyl resins; phenols and / or naphtho Dicyclopentadiene type phenol resin; triphenylmethane type phenol resin; terpene modified phenol resin; paraxylylene and / or metaxylylene modified phenol resin; melamine modified phenol resin; And the phenol resin obtained by copolymerizing these 2 or more types is mentioned. These may be used alone or in combination of two or more.

  Among the above curing agents, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, anhydrous It is preferable to use diethyl glutaric acid or 1,3,5-tris (3-carboxypropyl) isocyanurate. These may be used alone or in combination of two or more.

  The content of the curing agent in the thermosetting resin composition for light reflection is (A) an active group (acid) in the curing agent that can react with the epoxy group with respect to 1 equivalent of the epoxy group in the epoxy resin. (Anhydride group or hydroxyl group) is preferably in a ratio such that 0.5 to 1.2 equivalents, and more preferably in a ratio such that 0.6 to 1.0 equivalents. When the active group is less than 0.5 equivalents, the curing rate of the light-reflective thermosetting resin composition is slowed, and the glass transition temperature of the resulting cured product is lowered, so that a sufficient elastic modulus is obtained. There may not be. On the other hand, when the active group exceeds 1.2 equivalents, the strength after curing may decrease.

((C) component; white pigment)
Examples of the white pigment include alumina, magnesium oxide, antimony oxide, titanium oxide, zinc oxide, zirconium oxide, and inorganic hollow particles. These may be used alone or in combination of two or more. From the viewpoint of thermal conductivity and light reflection characteristics, it is preferable to use titanium oxide.

  Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu.

  The center particle diameter of the white pigment is preferably in the range of 0.1 μm to 50 μm, more preferably 0.1 to 20 μm, and still more preferably 0.1 to 5 μm. If the center particle diameter is 0.1 μm or more, the particles tend not to aggregate and tend to be excellent in dispersibility, and if it is 50 μm or less, the light reflection characteristics of the cured product can be easily obtained. The center particle size of the white pigment can be measured with a commercially available particle size distribution meter utilizing a light scattering phenomenon.

  It is preferable that the content of the white pigment in the thermosetting resin composition for light reflection is in the range of 10 to 85% by volume based on the total amount of the resin composition. When the content of the white pigment is 10% by volume or more, the light reflection property of the cured product is easily obtained, and when it is 85% by volume or less, the moldability of the thermosetting resin composition is improved, and the optical semiconductor element. It becomes easy to produce a mounting substrate.

  The thermosetting resin composition for light reflection can further contain various additives such as an inorganic filler, an antioxidant, a release agent, a dispersant, and an ion scavenger in addition to the components described above.

  Examples of the inorganic filler include fused spherical silica, crushed silica, silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. The center particle diameter of the inorganic filler is preferably in the range of 1 to 100 μm, more preferably 1 to 50 μm, and more preferably 1 to 30 μm from the viewpoint of improving the packing efficiency with the white pigment. Further preferred. The center particle size of the inorganic filler can be measured with a commercially available particle size distribution meter utilizing a light scattering phenomenon. The content of the inorganic filler in the light-reflective thermosetting resin composition is preferably in the range of 5 to 75% by volume based on the total amount of components that become solid after the thermosetting resin composition is cured.

  A coupling agent or the like may be added to the thermosetting resin composition for light reflection as necessary. In this case, the interfacial adhesion between the resin component such as the component (A) and the inorganic component such as the white pigment and the inorganic filler 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-based, amino silane-based, cationic silane-based, vinyl silane-based, acrylic silane-based or mercapto silane-based coupling agents, or composite coupling agents thereof are used. Can be used. The amount of the coupling agent used is preferably adjusted as appropriate in consideration of the surface coating amount on the white pigment, but from the viewpoint of improving curability, the amount used is 5% by mass or less based on the total amount of the thermosetting resin composition. It is preferable. A white pigment, an inorganic filler, or the like may be previously treated with the coupling agent.

  The light-reflective thermosetting resin composition preferably has a light reflectance at a wavelength of 350 to 800 nm after curing of 80% or more because of its use. When this light reflectance is less than 80%, there is a tendency that it cannot sufficiently contribute to the improvement of the luminance of the optical semiconductor device. The light-reflective thermosetting resin composition preferably has a light reflectance of 90% or more. Further, in terms of improving the luminance of the optical semiconductor device, the light reflectance after curing at a wavelength of 460 nm is preferably 80% or more, and more preferably 90% or more.

  From the viewpoint of improving the heat-resistant coloring property, the molded product after curing can maintain a light reflectance of 80% or more at a wavelength of 350 to 800 nm even after a heat resistance test that is exposed to an environment of 150 ° C. for 500 hours. Preferably, the light reflectance at a wavelength of 460 nm is more preferably 85% or more, and still more preferably 90% or more. The light reflection characteristics of such a thermosetting resin composition can be realized by appropriately adjusting the blending amounts of various components constituting the resin composition, more specifically, a colorless thermosetting resin. This can be achieved by high loading of the components and the high refractive index white pigment.

  The thermosetting resin composition for light reflection can be prepared by uniformly dispersing and mixing the various components described above, and the mixing means and conditions are not particularly limited. As a preparation method, for example, various components are kneaded using a stirring and mixing device that combines rotation and revolution, such as a mixing roll, an extruder, a kneader, a roll, an extruder, a raking machine, and then the obtained kneading The method of cooling and grinding | pulverizing a thing is mentioned. The kneading type is not particularly limited, but melt kneading is preferable. The conditions at the time of melt-kneading may be appropriately determined depending on the type or blending amount of various components to be used, and are not particularly limited. For example, the melt kneading is preferably performed at a temperature range of 15 to 100 ° C. for 5 to 40 minutes, more preferably at a temperature range of 20 to 100 ° C. for 10 to 30 minutes. When the melt kneading temperature is 15 ° C. or higher, various components are sufficiently easily melt kneaded, and the dispersibility tends to be improved. On the other hand, when the melt-kneading is 100 ° C. or lower, it becomes difficult to increase the molecular weight of the resin composition, and the resin composition can be prevented from being cured before the molded product is molded. Further, if the melt-kneading time is 1 minute or longer, the resin is less likely to ooze out from the mold during molding, and burrs tend not to occur. If it is 40 minutes or shorter, the resin composition is polymerized. It becomes difficult to progress and it can prevent that a resin composition hardens | cures before shaping | molding.

  When preparing a thermosetting resin composition for light reflection, when a curing agent is blended, a compound used as a curing agent may be premixed with a part or all of the epoxy resin (A). By carrying out such premixing, the dispersibility of the curing agent with respect to the base resin can be further enhanced. As a result, it is possible to more effectively suppress the occurrence of mold and package contamination due to the dispersion failure of the curing agent.

  (A) Although premixing may be performed between the total amount of the epoxy resin and the compound used as the curing agent, (A) sufficient effect can be obtained even by premixing with a part of the epoxy resin. It is done. In that case, the amount of the (A) epoxy resin used for the preliminary mixing is preferably 10 to 50% by mass of the total amount of the components.

  The premixing method is not particularly limited as long as the compound used as the curing agent can be dispersed in the (A) epoxy resin. For example, a method in which both components are stirred for 0.5 to 20 hours under a temperature condition of room temperature to 220 ° C. From the viewpoint of dispersibility and efficiency, the stirring time is preferably 1 to 10 hours, more preferably 3 to 6 hours, preferably at a temperature of 100 to 200 ° C., more preferably 150 to 170 ° C. it can. For example, (A) 100 parts by mass of epoxy resin and 120 parts by mass of curing agent are weighed in a heat-resistant glass container, and the mixing container is a heater using a fluid such as silicone oil or water as a medium. The method of heating in the temperature range of 35-180 degreeC using is mentioned. The heating method is not limited to the above method, and a known method such as thermocouple or electromagnetic wave irradiation can be used, and ultrasonic wave or the like may be irradiated to further promote dissolution.

[Optical semiconductor device mounting substrate]
The substrate for mounting an optical semiconductor element according to the present embodiment has a recess composed of a bottom surface and a wall surface. 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, of the thermosetting resin composition for light reflection according to the above embodiment It consists of a cured 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, the metal wiring 105 on which the Ni / Ag plating 104 is formed, and the recess 200 formed from the resin molded body 103 ′ and the reflector 103. have. 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 made of a cured product of the light reflecting thermosetting resin composition according to the above-described 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 using the thermosetting resin composition for light reflection. FIG. 2 is a schematic view showing an embodiment of a process for manufacturing a substrate for mounting an optical semiconductor element. The optical semiconductor element mounting substrate 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 (FIG. 2A), The metal wiring 105 is placed in a mold 151 having a predetermined shape, a light-reflective thermosetting resin composition is injected from a resin injection port 150 of the mold 151, and transfer molding is performed under predetermined conditions (FIG. 2B). )) And a step of removing the mold 151 (FIG. 2C). In this manner, the optical semiconductor element mounting region (concave 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 light-reflective thermosetting resin composition. . The bottom surface of the recess is made of a metal wiring 105 serving as a first connection terminal and a metal wiring 105 serving as a second connection terminal, and a cured product of a light-reflective thermosetting resin composition provided therebetween. Insulating resin molded body 103 ′. In addition, as the conditions for the transfer molding, the mold temperature is 170 to 200 ° C., more preferably 170 to 190 ° C., the molding pressure is 0.5 to 20 MPa, more preferably 2 to 8 MPa, and the after cure temperature is 60 to 120 seconds. 1 to 3 hours are preferable at 120 ° C to 180 ° C.

[Optical semiconductor device]
The optical semiconductor device according to the present embodiment includes the optical semiconductor element mounting substrate and an optical semiconductor element mounted on the optical semiconductor element mounting substrate. As a more specific example, the optical semiconductor element mounting substrate, the optical semiconductor element provided in the recess of the optical semiconductor element mounting substrate, and the phosphor-containing envelope that fills the recess 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. A sealing resin portion made of a transparent sealing resin 101 including a phosphor 106 that fills and seals the optical semiconductor element, and the optical semiconductor element 100 and the metal wiring 105 on which the Ni / Ag plating 104 is formed; Are electrically connected by bonding wires 102 or solder bumps 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.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this. For example, the thermosetting resin composition for light reflection of the present invention can be used as a light reflection coating agent. As this embodiment, a copper-clad laminate, an optical semiconductor element mounting substrate, and an optical semiconductor element will be described.

  The copper clad laminate according to the present embodiment includes a light reflecting resin layer formed using the above-described thermosetting resin composition for light reflection, and a copper foil laminated on the white resin layer. It is.

  FIG. 7 is a schematic cross-sectional view showing a preferred embodiment of a copper clad laminate. As shown in FIG. 7, a copper clad laminate 400 includes a base material 401, a white resin layer 402 laminated on the base material 401, and a copper foil 403 laminated on the white resin layer 402. I have. Here, the white resin layer 402 is formed using the above-described thermosetting resin composition for light reflection of the present invention.

  Although the base material used for a copper clad laminated board can be especially used as the base material 401 without a restriction | limiting, For example, resin laminated boards, such as an epoxy resin laminated board, a board | substrate for optical semiconductor mounting, etc. are mentioned.

  The copper-clad laminate 400 is produced, for example, by applying a resin composition to the surface of the base material 401, stacking copper foils 403, and heating and pressing to form a white resin layer 402 made of the resin composition. be able to.

  As a method for applying the resin composition to the substrate 401, for example, a coating method such as a printing method, a die coating method, a curtain coating method, a spray coating method, or a roll coating method can be used. At this time, the light-reflective thermosetting resin composition can contain a solvent so as to facilitate application. In addition, when using a solvent, about the thing based on the resin composition whole quantity by the mixture ratio of each component mentioned above, it is preferable to set what remove | excluded the solvent as a whole quantity.

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

  Using the copper-clad laminate, a printed wiring board for an optical member such as an LED can be produced. The copper clad laminate 400 shown in FIG. 7 is obtained by laminating a white resin layer 402 and a copper foil 403 on one side of a base material 401, but the copper clad laminate is a white resin on both sides of the base material 401. The layer 402 and the copper foil 403 may be laminated. Further, the copper-clad laminate may be composed of only the white resin layer 402 and the copper foil 403 without using the base material 401. In this case, the white resin layer 402 plays a role as a base material. In this case, for example, a white resin layer 402 can be obtained by impregnating a resin composition into glass cloth or the like and curing the resin composition.

  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 type light emitting diode including an optical semiconductor element 410 and a transparent sealing resin 404 provided so as to seal the optical semiconductor element 410. is there. In the optical semiconductor device 500, the 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 a wire 409.

  Furthermore, as another embodiment of the substrate for mounting an optical semiconductor element, a white resin layer formed between a plurality of conductor members (connection terminals) on a base material using the above-described thermosetting resin composition for light reflection. And an optical semiconductor element mounting substrate. In another embodiment of the optical semiconductor device, the optical semiconductor element is mounted on the optical semiconductor element mounting substrate.

  FIG. 9 is a schematic cross-sectional view showing a preferred embodiment of an optical semiconductor device. As shown in FIG. 9, the optical semiconductor device 600 is formed between a base member 601, a plurality of conductor members 602 formed on the surface of the base member 601, and a plurality of conductor members (connection terminals) 602. An optical semiconductor element 610 is mounted on a substrate for mounting an optical semiconductor element comprising a white resin layer 603 made of the thermosetting resin composition for light reflection, and is transparent so that the optical semiconductor element 610 is sealed. A surface-mount light emitting diode provided with a sealing resin 604. 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 wire 609.

  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 a white color made of the above-described thermosetting resin composition for light reflection, which is obtained by applying a thermosetting resin composition for light reflection between a plurality of conductor members 602 on a base material 601 and curing by heating. It can be manufactured by forming the resin layer 603.

  As a method for applying the light-reflective thermosetting resin composition to the substrate 601, for example, a coating method such as a printing method, a die coating method, a curtain coating method, a spray coating method, or a roll coating method can be used. At this time, the light-reflective thermosetting resin composition can contain a solvent so as to facilitate application. In addition, when using a solvent, about the thing based on the resin composition whole quantity by the mixture ratio of each component mentioned above, it is preferable to set what remove | excluded the solvent as a whole quantity.

  Although it does not specifically limit as heating conditions at the time of heat-hardening the coating film of the thermosetting resin composition for light reflections, For example, it is preferable to heat on 130-180 degreeC and the conditions for 30 to 600 minutes.

  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.

  In order to ensure adhesion between the white resin layer 603 and the conductor member 602, it is also preferable to subject the conductor member 602 to a roughening treatment such as oxidation-reduction treatment or CZ treatment (manufactured by MEC Co., Ltd.).

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

<Synthesis of polyorganosiloxane having epoxy group>
(Synthesis Example 1)
In a glass container, 48 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 51 g of phenyltrimethoxysilane, 1.0 g of methyltrimethoxysilane and 100 g of toluene are stirred and dissolved, 0.11 g Of potassium hydroxide and 5.0 g of distilled water were added to initiate reflux. Methanol and water produced by the condensation were distilled off, and the mixture was cooled when the distillation of water stopped. Acetic acid was added dropwise to the system for neutralization, and the produced potassium acetate was filtered off, and then toluene was distilled off from the filtrate to obtain 95 g of a polyorganosiloxane having a colorless solid epoxy group. The obtained polyorganosiloxane having an epoxy group had a Mn of 1700, a softening point of 60 ° C. and an epoxy group equivalent of 360. The obtained product was incompatible with hexahydrophthalic anhydride used as a curing agent in the range of 40 to 180 ° C.

<Preparation of thermosetting resin composition for light reflection>
(Examples 1-6 and Comparative Examples 1-7)
Each component was blended according to the blending ratio (parts by mass) shown in Table 1 and Table 2, and sufficiently kneaded and dispersed with a mixer, and then melt-kneaded with a mixing roll at 135 ° C. for 15 minutes to obtain a kneaded product. Next, the obtained kneaded material was cooled and pulverized, thereby preparing a white solid light-reflective thermosetting resin composition.

  In addition, the unit of the compounding quantity of each raw material shown to each table | surface is all mass parts, and the description part of "-" means that there is no mixing | blending of a corresponding raw material.

The details of * 1 to 9 in Tables 1 and 2 are as follows.
* 1: Fluorinated epoxy resin (Mitsubishi Chemical Corporation, trade name: YL7702, in formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, n = 0, Mn 500, epoxy equivalent 238 g / eq)
* 2: Polyorganosiloxane having an epoxy group (Synthesis Example 1)
* 3: Trisglycidyl isocyanurate (manufactured by Nissan Chemical Industries, trade name: TEPIC-S, Mn300, epoxy equivalent 100 g / eq, softening point 110 ° C.)
* 4: Hexahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd., trade name: HH)
* 5: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: PX-4ET)
* 6: Dimethyl-p-acetoxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150)
* 7: Fused silica (Electrochemical Industry Co., Ltd., trade name: FB-950)
* 8: Fused silica (manufactured by Admatechs Co., Ltd., trade name: SO-25R)
* 9: Titanium oxide (Ishihara Sangyo Co., Ltd., trade name: CR63)

<Evaluation of thermosetting resin composition for light reflection>
After transfer molding the light-reflective thermosetting resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 under the conditions of a molding die temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Then, post-curing was performed at 150 ° C. for 2 hours to prepare a test piece having a thickness of 1.0 mm. Using the obtained test piece, the light reflectance after the initial stage and after the heat treatment was measured according to the following method. In Comparative Examples 1, 2, and 7, a molded body could not be produced.

(Measurement of light reflectance)
[initial]
About the test piece obtained above, the light reflectance in wavelength 460nm was measured using integrating sphere type spectrophotometer CM600d (made by Konica Minolta Co., Ltd.).

[After heat treatment]
The test piece obtained above was put in an oven at a constant temperature and subjected to heat treatment under the conditions shown in the table. About the test piece after each heat processing, the light reflectivity was measured like the above.

(Measurement of moisture resistance)
The test piece obtained above was left in an environment of 85 ° C. and 85% RH for 168 hours using a constant temperature and humidity chamber, and the weight change before and after being left was measured. The ratio of the moisture absorption increased before and after standing to the weight of the test piece was defined as the moisture absorption rate.

  As shown in Table 1, according to the thermosetting resin compositions of Examples 1 to 6, a molded body having a sufficiently high light reflectance is obtained by transfer molding, and the reflectance decreases after heat treatment of the molded body, that is, It was confirmed that coloring can be highly suppressed. Moreover, it was confirmed that the thermosetting resin composition of Examples 1-6 has a small moisture absorption rate and is excellent in moisture resistance.

  DESCRIPTION OF SYMBOLS 100 ... Optical semiconductor element, 101 ... Transparent sealing resin, 102 ... Bonding wire, 103 ... Hardened | cured material (reflector) of the thermosetting resin composition for light reflection, 103 '... Curing of the thermosetting resin composition for light reflection Article (insulating resin molding) 104 ... Ni / Ag plating, 105 ... metal wiring, 106 ... phosphor, 107 ... solder bump, 110 ... substrate for mounting optical semiconductor element, 150 ... resin injection port, 151 ... mold, DESCRIPTION OF SYMBOLS 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 ... base material, 402 ... white resin layer, 403 ... copper foil, 404 ... sealing resin, 408 ... adhesive layer, 409 ... wire, 410 ... optical semiconductor element, 50 , 600 ... optical semiconductor device, 601 ... substrate, 602 ... conductor member, 603 ... white resin layer, 604 ... sealing resin, 608 ... adhesive layer, 609 ... wire, 610 ... optical semiconductor element.

Claims (12)

Including epoxy resin, curing catalyst and white pigment,
The epoxy resin contains a fluorinated epoxy resin represented by the following general formula (1) and a polyorganosiloxane having an epoxy group ,
A thermosetting resin composition for light reflection , wherein the polyorganosiloxane having an epoxy group is a condensate of a silane compound having an epoxy group and a silane compound not having an epoxy group .

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents a number from 0 to 40. ] The thermosetting resin composition for light reflection according to claim 1 , wherein an epoxy equivalent of the polyorganosiloxane having an epoxy group is 150 to 500 g / eq. The light-reflective thermosetting resin composition according to claim 1 or 2 , wherein the polyorganosiloxane having an epoxy group has a number average molecular weight of 300 to 5,000. The thermosetting resin composition for light reflection according to any one of claims 1 to 3 , further comprising a curing agent. The said white pigment contains at least 1 sort (s) chosen from the group which consists of an alumina, magnesium oxide, antimony oxide, titanium oxide, a zinc oxide, a zirconium oxide, and an inorganic hollow particle, It is any one of Claims 1-4. The thermosetting resin composition for light reflection. The thermosetting resin composition for light reflection according to any one of claims 1 to 5 , wherein the white pigment has a center particle diameter of 0.1 to 50 µm. The thermosetting resin composition for light reflection according to any one of claims 1 to 6 , wherein the content of the white pigment is 10 to 85% by volume based on the total amount of the thermosetting resin composition. A substrate for mounting an optical semiconductor element, comprising a cured product of the thermosetting resin composition for light reflection according to any one of claims 1 to 7 . It has a recess composed of a bottom surface and a wall surface, and the bottom surface of the recess is a mounting portion for an optical semiconductor element,
The substrate for mounting an optical semiconductor element, wherein at least a part of the wall surface of the concave portion is a cured product of the thermosetting resin composition for light reflection according to any one of claims 1 to 7 . A substrate,
A first connection terminal and a second connection terminal provided on the substrate;
The cured product of the thermosetting resin composition for light reflection according to any one of claims 1 to 7 , provided between the first connection terminal and the second connection terminal,
A substrate for mounting an optical semiconductor element. An optical semiconductor device comprising: the optical semiconductor element mounting substrate according to any one of claims 8 to 10 ; and an optical semiconductor element mounted on the optical semiconductor element mounting substrate. A method of manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface,
A substrate for mounting an optical semiconductor element comprising a step of forming at least a part of the wall surface of the concave portion by transfer molding the thermosetting resin composition for light reflection according to any one of claims 1 to 7. Manufacturing method.

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