JP5699443B2 - 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, a substrate for mounting an optical semiconductor element, a method for manufacturing the same, and an optical semiconductor device.

  An optical semiconductor device combining an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor is high in energy efficiency and has a long life, so it is used for outdoor displays, portable liquid crystal backlights, and in-vehicle applications. The demand is expanding. As a result, the brightness of LED devices is increasing, and it is required to prevent an increase in junction temperature due to an increase in the amount of heat generated by the element and deterioration of the optical semiconductor device due to a direct increase in light energy.

  Patent Document 1 discloses an optical semiconductor element mounting substrate and an optical semiconductor device using a thermosetting resin composition containing an acid anhydride as a curing agent as a reflector material.

JP 2006-140207 A

  Conventionally, as a method of forming a reflector from a thermosetting resin composition, for example, a method of forming a thermosetting resin composition into a tablet and then performing transfer molding is proposed.

  Examples of a method for molding a tablet from the thermosetting resin composition include a method as shown in FIG. That is, a step of supplying a raw material of the thermosetting resin composition (raw material supply step), a step of heating and melting the raw material and mixing (kneading step), and a step of cooling the thermosetting resin composition after kneading (cooling) Step), a step of crushing the thermosetting resin composition after cooling (crushing step), a step of putting the pulverized thermosetting resin composition powder into a molding die and tableting to obtain a tablet (tablet step) ).

  By the way, from the viewpoint of improving the productivity of tablets, it is required to perform these steps continuously.

However, in the above pulverization step, if the thermosetting resin composition has adhesiveness, it may adhere to the pulverizer and may be difficult to pulverize. In the tableting step, the powder may adhere to the surface of the molding die, and the tablet may be destroyed when tableting.

  The present invention has been made in view of the above-described problems of the prior art, has a rigidity that can be pulverized in the vicinity of room temperature, and has sufficiently reduced adhesion to a processing apparatus and a molding apparatus. An object is to provide a resin composition, a substrate for mounting an optical semiconductor using the resin composition, a method for manufacturing the substrate for mounting an optical semiconductor, and an optical semiconductor device.

  As a result of intensive studies to achieve the above object, the inventors of the present invention (B) use an organic acid anhydride having a melting point of 100 ° C. or higher as the curing agent, so that the rigidity can be pulverized near room temperature. It has been found that a thermosetting resin composition having a sufficient adhesion to a processing apparatus and a molding apparatus can be obtained, and the present invention has been completed.

  That is, the present invention is a thermosetting resin composition containing (A) an epoxy resin, (B) a curing agent and (C) a white pigment, and the (B) curing agent has a melting point of 100 ° C. or higher. Provided is a light-reflective thermosetting resin composition containing an organic acid anhydride.

  Here, when the organic acid anhydride is a non-aromatic compound, the effects of the present invention can be expressed more effectively and reliably.

  The organic acid anhydride is more preferably an organic acid anhydride having a Hazen color number of 50 or less. Thereby, when the hardened | cured material of the thermosetting resin composition of this invention is used for the board | substrate for optical semiconductor mounting, the reflectance of light improves and the brightness | luminance of an optical semiconductor device can be improved.

  The organic acid anhydride can contain at least one acid anhydride selected from the group consisting of compounds represented by the following formulas (1), (2), (3) and (4).

  In the succinic anhydride represented by the above formula (1), the hydrogenated pyromellitic anhydride represented by the above formula (2), the hydrogenated biphenyl dianhydride represented by the above formula (3), and the above formula (4) By using at least one of the tetrahydrophthalic anhydrides represented as a curing agent, the effects of the present invention can be reliably obtained.

  Moreover, it is preferable that content of the said organic acid anhydride is 3-100 mass% on the basis of the mass of the said (B) hardening | curing agent.

  The white pigment (C) preferably contains at least one inorganic substance selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles.

  In the thermosetting resin composition of the present invention, (C) a white pigment containing at least one inorganic substance selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide and inorganic hollow particles is used. Thereby, the reflective characteristic of the hardened | cured material of a thermosetting resin composition can be ensured, and the performance as an optical material can fully be exhibited.

  Furthermore, the present invention 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, and at least a part of the wall surface of the recess is a cured product of the thermosetting resin composition. An optical semiconductor element mounting substrate is provided.

  Furthermore, the manufacturing method of the board | substrate for optical semiconductor element mounting provided with the process of forming at least one part of the wall surface of a recessed part using the said thermosetting resin composition is provided.

  Furthermore, an optical semiconductor element mounting substrate having a recess composed of a bottom surface and a wall surface, an optical semiconductor element provided in the recess of the optical semiconductor element mounting substrate, and the optical semiconductor element filled with the recess An optical semiconductor device comprising: a sealing resin portion that seals, wherein at least a part of the wall surface of the recess is made of a cured product of the thermosetting resin composition.

  According to the present invention, a light-reflective thermosetting resin composition having rigidity enough to be pulverized near room temperature and sufficiently reduced adhesion to a processing apparatus or a molding apparatus, and an optical semiconductor using the resin composition A mounting substrate, an optical semiconductor mounting substrate manufacturing method, and an optical semiconductor device can be provided.

It is a flowchart which shows the process of producing a tablet from a thermosetting resin composition. It is the schematic which shows the process of producing the raw material powder of a tablet from a thermosetting resin composition. It is a schematic sectional drawing which shows the process of shape | molding the tablet produced from the thermosetting resin composition. It is a perspective view which shows one Embodiment of the board | substrate for optical semiconductor element mounting of this invention. It is the schematic which shows one Embodiment of the process of manufacturing the board | substrate for optical semiconductor element mounting of this invention. It is a perspective view which shows one Embodiment of the state which mounted the optical semiconductor element in the board | substrate for optical semiconductor element mounting of this invention. 1 is a schematic cross-sectional view showing an embodiment of an optical semiconductor device of the present invention. It is a schematic cross section which shows other one Embodiment of the optical semiconductor device of this invention. It is a schematic cross section which shows other one Embodiment of the optical semiconductor device of this invention.

    Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In addition, “(meth) acrylate” in the present specification means “acrylate” or “methacrylate” corresponding thereto.

  The thermosetting resin composition of the present invention contains (A) an epoxy resin (B) curing agent and (C) a white pigment, and the (B) curing agent contains an organic acid anhydride having a melting point of 100 ° C. or higher. It is characterized by including. Hereafter, the structural component of the thermosetting resin composition of this invention is explained in full detail.

<(A) Epoxy resin>
As (A) epoxy resin in the thermosetting resin composition of this invention, what is generally used with the epoxy resin molding material for electronic component sealing can be used. Epoxy resins include, for example, epoxidized phenol and aldehyde novolak resins such as phenol novolac type epoxy resin and orthocresol novolak type epoxy resin, diglycidyl such as bisphenol A, bisphenol F, bisphenol S and alkyl substituted bisphenol Glycidylamine type epoxy resin obtained by reaction of polyamine such as ether, diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, and alicyclic An epoxy resin is mentioned. These can be used alone or in combination of two or more.

  Among these, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Dicarboxylic acid diglycidyl ester derived from epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate and 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid This is preferable because of less coloration. For the same reason, diglycidyl esters of dicarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid and methylnadic acid are also suitable. Examples thereof include glycidyl esters such as nuclear hydrogenated trimellitic acid and nuclear hydrogenated pyromellitic acid having an alicyclic structure in which an aromatic ring is hydrogenated. Polyorganosiloxane having an epoxy group produced by heating and hydrolyzing and condensing a silane compound in the presence of an organic solvent, an organic base and water is also included. Further, as the epoxy resin (A), an epoxy resin represented by the following formula (5), which is a copolymer of a glycidyl (meth) acrylate monomer and a polymerizable monomer, can also be used. .

In Formula (5), R ¹ represents a glycidyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms. , R ⁴ represents a monovalent saturated hydrocarbon group. a and b represent a positive integer.

  (A) The epoxy resin is 1,2-epoxy-4- (2-oxiranyl) of 2,2-bis (hydroxymethyl) -1-butanol from the viewpoint of suppressing the contamination of the thermosetting resin composition of the present invention. A cyclohexane adduct is preferable, and a product name: EHPE3150 manufactured by Daicel Chemical Industries, Ltd. is commercially available.

  In addition, (A) the epoxy resin contains cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane in order to suppress coloring of the cured product of the thermosetting resin composition of the present invention. An alicyclic epoxy resin having an aliphatic hydrocarbon group derived by removing a hydrogen atom from a cyclic aliphatic hydrocarbon selected from hydrogenated hydronaphthalene and hydrogenated biphenyl is also preferred. The cycloaliphatic hydrocarbon may be substituted with a halogen atom or a linear or branched hydrocarbon group.

<(B) Cured product>
In the thermosetting resin composition of the present invention, the (B) curing agent contains an organic acid anhydride having a melting point of 100 ° C. or higher. Thereby, the thermosetting resin composition which has the rigidity which can be grind | pulverized near room temperature (0 degreeC-30 degreeC), and also reduced fully the adhesion to a processing apparatus or a shaping | molding apparatus can be obtained. In the present invention, “an organic acid anhydride having a melting point of 100 ° C. or higher” means an organic acid anhydride that is solid at a temperature lower than 100 ° C., and includes organic acid anhydrides that are softened and decomposed at 200 ° C. or higher. .

  In addition, when the mixture obtained by heating and melting a thermosetting resin composition containing (A) an epoxy resin or (B) a curing agent having a low melting point or a low softening point is cooled again, The time until the curable resin composition is solidified can be shortened.

  Here, the organic acid anhydride is preferably a non-aromatic compound. Thereby, said effect can be acquired reliably.

  Examples of the organic acid anhydride include compounds represented by the following formulas (1) to (4), respectively.

  The thermosetting resin composition according to the present invention includes a succinic anhydride represented by the above formula (1), a hydrogenated pyromellitic anhydride represented by the above formula (2), and a hydrogenated biphenyl represented by the above formula (3). Of the acid dianhydride and the tetrahydrophthalic anhydride represented by the above formula (4), the above effect can be obtained with certainty by using at least one acid anhydride as a curing agent.

  The compound represented by the above formula (1) has a melting point of 120 to 130 ° C., and the compounds represented by the above formulas (2) and (3) are not clear but have a solid at a temperature below 100 ° C. The compound represented by the above formula (4) has a melting point of 110 to 120 ° C. These compounds have high crystallinity, and by mixing these compounds, solidification is promoted when allowed to stand at room temperature after heating and mixing, and handling such as workability and pulverization is facilitated.

  The Hazen color number of the organic acid anhydride is preferably 50 or less, and more preferably 20 or less. Thereby, when the hardened | cured material of the thermosetting resin composition of this invention is used for the board | substrate for optical semiconductor mounting, the reflectance of light improves and the brightness | luminance of an optical semiconductor device can be improved.

  Here, the Hazen color number is a value measured in accordance with ASTM D1209-1980 (American Standards Association Standard). The color number standard solution was prepared by dissolving 1.245 g of potassium platinum chloride (IV) (0.500 g as platinum) and 1.000 g of cobalt chloride (II) hexahydrate (0.250 g as cobalt) in 100 ml of hydrochloric acid. Further, it is diluted to 1000 ml with distilled water to obtain a color number standard solution having a Hazen color number of 500. Hazen color number standard solutions such as 100, 50, 20, 10, etc. can be obtained by diluting a Hazen color number standard solution of 500, 5, 10, 25, 50 times with distilled water, respectively. . The Hazen color number is indicated by the number of the color standard solution having the same feeling when the sample is put in a test tube (diameter: 3 cm, length: about 20 cm) of a prescribed size and visually compared. When observed from the upper surface of the test tube, it is expressed as Hazen color number (APHA). APHA is an abbreviation for American Public Health Association.

  In the thermosetting resin composition of the present invention, the compound represented by the above formulas (1) to (4) may be included in the (B) curing agent, and the compounds shown below are included. May be. However, in order to sufficiently obtain the effects of the present invention, the content of the organic acid anhydride according to the present invention is preferably 3 to 100% by mass based on the mass of the (B) curing agent.

  In the thermosetting resin composition of the present invention, the (B) curing agent may contain a polyvalent carboxylic acid condensation condensate obtained by condensing two or more polyvalent carboxylic acids. “Polyvalent carboxylic acid condensate” means a polymer formed by condensing one or more polycarboxylic acids having two or more carboxyl groups between molecules. More specifically, the polyvalent carboxylic acid condensate has an acid anhydride group (an acid anhydride bond) formed by dehydration condensation between carboxy groups of two or more monomers having two or more carboxy groups. ) And each monomer unit is linked in a chain or cyclic manner by the generated acid anhydride group. The polycarboxylic acid condensate is usually composed of a plurality of components having different degrees of polymerization, and the constitution of repeating units and terminal groups is different. The proportion of the component represented by the following formula (6) is 60% by mass or more based on the total amount of the polyvalent carboxylic acid condensate.

In the above formula (6), R _x is a divalent organic group, R _y is a monovalent organic group, and n ¹ represents an integer of 1 or more. n ¹ is preferably an integer of 1 to 200.

R _x is preferably a divalent saturated hydrocarbon group having a saturated hydrocarbon ring. When R _x is a saturated hydrocarbon group having a saturated hydrocarbon ring, the polyvalent carboxylic acid condensate can form a transparent cured product of an epoxy resin. A plurality of R _x in the same molecule may be the same or different. The saturated hydrocarbon ring of R _x may be substituted with a halogen atom or a linear or branched hydrocarbon group. The hydrocarbon group that substitutes the saturated hydrocarbon ring is preferably a saturated hydrocarbon group. The saturated hydrocarbon ring may be a single ring or a condensed ring, a polycyclo ring, a spiro ring or a ring assembly composed of two or more rings. R _x preferably has 3 to 15 carbon atoms.

R _x is a group derived by removing a carboxyl group from a polyvalent carboxylic acid as a monomer used to obtain the component (polymer) represented by the above formula (6). The polyvalent carboxylic acid as a monomer preferably has a boiling point higher than the reaction temperature of polycondensation.

More specifically, R _x is hydrogen from a cycloaliphatic hydrocarbon selected from cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated hydronaphthalene and hydrogenated biphenyl. A divalent group derived by removing an atom is preferable. When R _x is these groups, the effect of obtaining a cured product that is transparent and less colored by heat is more remarkably exhibited. These cyclic saturated hydrocarbons may be substituted with a halogen atom or a linear or branched hydrocarbon group (preferably a saturated hydrocarbon group).

In particular, R _x is preferably a group derived by removing a carboxyl group from 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or derivatives thereof. That is, R _x is preferably a divalent group represented by the following formula (7). In following formula (7), m shows the integer of 0-4. R _z represents a halogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms. When m is 2 to 4, a plurality of R _z may be the same or different, and may be connected to each other to form a ring.

R _y which is a terminal group in the above formula (6) represents a monovalent hydrocarbon group which may be substituted with an acid anhydride group or a carboxylic ester group. Two R _y may be the same or different. R _y may be a monovalent group derived by removing a carboxyl group from a linear, branched, or cyclic C 2-15 aliphatic or aromatic monocarboxylic acid (benzoic acid or the like). Good.

R _y is preferably a monovalent group represented by the following formula (8), or cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene and hydrogen It is a monovalent group derived by removing a hydrogen atom from a cycloaliphatic hydrocarbon selected from conjugated biphenyl. By _Ry being these groups, the effect of obtaining a cured product with less coloring due to heat is more remarkably exhibited. Further, when R _y is such a group, the concentration of the carboxylic acid residue in the polyvalent carboxylic acid condensate can be reduced, and dispersion of the molecular weight can be suppressed.

R _x may be a divalent group represented by the above formula (7), and at the same time, R _y may be a monovalent group represented by the above formula (8). That is, the polyvalent carboxylic acid condensate according to the present embodiment may include a component represented by the following formula (1a) as the component represented by the above formula (6).

^{N 1} in the above formula (1a), similarly to the ^{n 1} of the formula (6) represents an integer of 1 or more, preferably 1 to 200 integer.

  The weight average molecular weight (Mw) of the polyvalent carboxylic acid condensate is preferably 200 to 20000. If Mw is less than 200, the viscosity tends to be too low to make it difficult to suppress the occurrence of contamination of the thermosetting resin composition during transfer molding of the thermosetting resin composition. There is a tendency that the compatibility of the thermosetting resin composition is lowered and the fluidity at the time of transfer molding of the thermosetting resin composition is lowered.

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

  The polyvalent carboxylic acid condensate can be obtained by dehydration condensation in a reaction solution containing a polyvalent carboxylic acid and a monocarboxylic acid used as necessary. For example, in a reaction solution containing a dicarboxylic acid represented by the following formula (9) and a monocarboxylic acid represented by the following formula (10), a method comprising a step of dehydrating and condensing each carboxyl group between molecules Can be obtained.

  The dehydrating condensation reaction liquid is, for example, a polyhydric carboxylic acid and a monocarboxylic acid, and a dehydrating agent selected from acetic anhydride or propionic anhydride, acetyl chloride, an aliphatic acid chloride, and an organic base (such as trimethylamine) that dissolve them. Containing. For example, after the reaction solution is refluxed in a nitrogen atmosphere for 5 to 60 minutes, the temperature of the reaction solution is increased to 180 ° C., and polycondensation is performed by distilling off the generated acetic acid and water in an open system under a nitrogen stream. To advance. When generation of volatile components is no longer observed, polycondensation proceeds in a molten state at a temperature of 180 ° C. for 3 hours, more preferably for 8 hours while reducing the pressure in the reaction vessel. The produced polyvalent carboxylic acid condensate may be purified by recrystallization or reprecipitation using an aprotic solvent such as acetic anhydride.

  In the dehydration condensation reaction, reaction conditions can be appropriately changed so as to obtain desired ICI corn plate viscosity, weight average molecular weight, and softening point, and the reaction conditions are not limited to the above. For example, the ICI cone plate viscosity, weight average molecular weight and softening point of the product are adjusted to desired values by the composition ratio of the polycarboxylic acid and monocarboxylic acid before the condensation reaction of the polycarboxylic acid condensate. Can do. As the ratio of polyvalent carboxylic acid increases, the ICI cone plate viscosity, weight average molecular weight, and softening point tend to increase.

  The polycarboxylic acid condensate is a condensate of two molecules of monocarboxylic acid, a condensate of polycarboxylic acid and monocarboxylic acid, an unreacted product of polycarboxylic acid and monocarboxylic acid, and acetic anhydride and There may be cases where a by-product such as an acid anhydride formed by a condensation reaction between a reaction reagent such as propionic anhydride and a polyvalent carboxylic acid or monocarboxylic acid is included. These by-products may be removed by purification, or may be used as a curing agent in a mixture.

  The softening point of the polyvalent carboxylic acid condensate is preferably 40 ° C to 180 ° C. When the softening point is less than 40 ° C., the handling property, kneading property and white pigment dispersibility are reduced during the production of the thermosetting resin composition, and the occurrence of contamination of the thermosetting resin composition during transfer molding is effectively prevented. There is a tendency to be difficult to suppress. When the softening point exceeds 180 ° C., the curing agent may remain undissolved in the resin composition when heated to 170 ° C. to 190 ° C. by transfer molding, and it tends to be difficult to obtain a uniform molded body.

  The softening point of the polyvalent carboxylic acid condensate can be set to a desired range by selecting the structure of the main chain and adjusting the weight average molecular weight. Generally, when a long-chain divalent carboxylic acid is used as a monomer, the softening point can be lowered, and when a highly polar structure is introduced, the softening point can be raised. In general, the softening point can be lowered by increasing the weight average molecular weight.

  In the thermosetting resin composition of the present invention, as the (B) curing agent, together with the polyvalent carboxylic acid condensate, a curing agent generally used in epoxy resin molding materials for electronic component sealing can be used in combination. . Such a curing agent is not particularly limited as long as it reacts with the epoxy resin, but is preferably colorless or light yellow. Examples of such a curing agent include an acid anhydride curing agent, an isocyanuric acid derivative curing agent, and a phenol curing agent.

  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, glutaric anhydride. Examples include acid, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, and methyl tetrahydrophthalic anhydride.

  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, 1,3-bis (2-carboxyethyl) isocyanurate.

  Among these 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. Moreover, the said hardening | curing agent may be used individually by 1 type or in combination of 2 or more types. When these curing agents that can be used in combination are included, the viscosity of the (B) curing agent as a whole can be adjusted by changing the blending ratio with the polyvalent carboxylic acid condensate, which is preferable.

  The above-described curing agent that can be used in combination preferably has a molecular weight of 100 to 400. In addition, an anhydride obtained by hydrogenating all unsaturated bonds of an aromatic ring is preferable to an acid anhydride having an aromatic ring such as trimellitic anhydride or pyromellitic anhydride. As the acid anhydride curing agent, an acid anhydride generally used as a raw material for the polyimide resin may be used.

  In the thermosetting resin composition of the present invention, the blending amount of the (B) curing agent is preferably 1 to 150 parts by mass with respect to 100 parts by mass of the (A) epoxy resin, and the thermosetting resin composition. From the viewpoint of suppressing the contamination of the cured product, it is more preferably 50 to 120 parts by mass.

  Further, (B) the curing agent has an active group (an acid anhydride group or a hydroxyl group) in (B) the curing agent capable of reacting with the epoxy group with respect to 1 equivalent of the epoxy group in (A) the epoxy resin. It is preferable to mix | blend so that it may become 0.5-0.9 equivalent, and it is more preferable that it will be 0.7-0.8 equivalent. If the said active group is less than 0.5 equivalent, while the cure rate of a thermosetting resin composition will become slow, the glass transition temperature of the hardened | cured material obtained will become low, and there exists a tendency for sufficient elasticity modulus to become difficult to be obtained. On the other hand, when the said active group exceeds 0.9 equivalent, there exists a tendency for the intensity | strength of hardened | cured material to fall.

<(C) White pigment>
In the thermosetting resin composition of the present invention, as the white pigment (C), a known pigment can be used and is not particularly limited. The (C) a white pigment, for example, Alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, antimony oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate, mica, beryllia, titanium Barium, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, etc., talc, aluminum borate , Aluminum borate, silicon carbide, and inorganic hollow particles. Among others, (C) a white pigment, the alumina, magnesium oxide, antimony oxide, titanium oxide, may comprise at least one inorganic material selected from the group consisting of zirconium oxide and inorganic hollow particles preferably. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu (white sand).

  When the thermosetting resin composition of the present invention contains (C) a white pigment, the cured product of the thermosetting resin composition has an excellent reflectance, and the light reflection provided in the substrate for mounting an optical semiconductor. When used as a material for an optical device, a high-brightness optical semiconductor device can be obtained.

  The white pigment preferably has a center particle size of 0.1 to 50 μm. When the center particle size is less than 0.1 μm, the particles tend to aggregate and the dispersibility tends to decrease, and when it exceeds 50 μm, it is difficult to sufficiently obtain the reflection characteristics of the cured product made of the thermosetting resin composition.

  (C) Although the compounding quantity of a white pigment is not specifically limited, It is preferable that it is 10-85 volume% with respect to the whole thermosetting resin composition, and it is more preferable that it is 20-75 volume%. If the blending amount is less than 10% by volume, the light-reflecting properties of the cured thermosetting resin composition tend not to be sufficiently obtained, and if it exceeds 85% by volume, the moldability of the thermosetting resin composition tends to be low. There is a tendency to decrease.

<Other ingredients>
(Curing accelerator)
A curing accelerator can be blended in the thermosetting resin composition of the present invention as necessary. As a hardening accelerator, if it has a catalyst function which accelerates | stimulates hardening reaction of (A) epoxy resin and (B) hardening | curing agent, it can use without being specifically limited. Examples of the curing accelerator include amine compounds, imidazole compounds, organic phosphorus compounds, alkali metal compounds, alkaline earth metal compounds, and quaternary ammonium salts. Among these curing accelerators, it is preferable to use an amine compound, an imidazole compound, or an organic phosphorus compound.

  Examples of the amine compound include 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, and tri-2,4,6-dimethylaminomethylphenol. Examples of the imidazole compound include 2-ethyl-4-methylimidazole. Examples of the organic phosphorus compound include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, tetra-n. -Butylphosphonium-tetraphenylborate. These curing accelerators may be used alone or in combination of two or more.

  The blending amount of the curing accelerator is preferably 0.01 to 8 parts by weight and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the (A) epoxy resin. When the content of the curing accelerator is less than 0.01 parts by mass, a sufficient curing acceleration effect may not be obtained. When the content exceeds 8 parts by mass, discoloration is observed in the cured product of the thermosetting oil and fat composition. There is a case.

(Coupling agent)
A coupling agent is preferably added to the thermosetting resin composition from the viewpoint of improving the adhesion between (A) the epoxy resin and (B) the curing agent and (C) the white pigment. Although it does not specifically limit as a coupling agent, For example, a silane coupling agent and a titanate coupling agent are mentioned. Examples of the silane coupling agent generally include epoxy silane, amino silane, cationic silane, vinyl silane, acryl silane, mercapto silane, and composites thereof, and can be used in any amount. In addition, it is preferable that the compounding quantity of a coupling agent is 5 mass% or less with respect to the whole thermosetting resin composition.

  Moreover, you may add additives, such as antioxidant, a mold release agent, and an ion capture agent, to the tree thermosetting fat composition of this embodiment as needed.

  The thermosetting resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above, and means and conditions thereof are not particularly limited.

  Hereinafter, a method for producing a cured product comprising the thermosetting resin composition of the present invention will be described. A cured product made of the thermosetting resin composition is produced, for example, by transfer molding the thermosetting resin composition. The thermosetting resin composition may be in any state such as liquid, solid, paste, etc., but is solid from the viewpoint of forming a tablet at the previous stage of injection molding into a molding die. It is preferable that it is a solid having rigidity.

  Here, as a preferred embodiment of the thermosetting resin composition of the present invention, a powder, a tablet comprising the thermosetting resin composition of the present invention, and a manufacturing method thereof will be described with reference to FIGS. . FIG. 2 is a schematic view showing a method for producing a powder as a raw material for tablets using the thermosetting resin composition of the present invention as a raw material. FIG. 3 is a schematic cross-sectional view showing a method for forming a tablet.

  The manufacturing method of the powder used as the raw material of the tablet of this embodiment comprises (I) raw material supply process, (II) kneading process, (III) sheeting process, and (IV) pulverization process.

(I) Raw material supply process The raw material which is a structural component of the thermosetting resin composition of this invention mentioned above is supplied to the raw material supply part 11. FIG.

(II) Kneading Step The raw material supplied from the raw material supply unit 11 is kneaded by a kneader 12 such as a kneader, a roll mill, or an extruder. When kneading the raw materials, it is preferable to use a kneader equipped with a screw in a molten state from the viewpoint of improving the dispersibility of each component. The kneading conditions may be appropriately determined depending on the type and blending amount of each component. For example, kneading is preferably performed at 40 ° C. to 150 ° C. for 0.5 to 40 minutes, and kneaded at 50 ° C. to 130 ° C. for 1 to 20 minutes. More preferably. When the kneading temperature is less than 40 ° C., it becomes difficult to knead each component and the dispersibility tends to decrease. When the kneading temperature exceeds 150 ° C., the resin composition is increased in molecular weight, and the resin composition is cured. There is a possibility that. If the kneading time is less than 5 minutes, resin burrs may be generated during transfer molding. If the kneading time exceeds 40 minutes, the resin composition may be increased in molecular weight and the resin composition may be cured.

  In the (II) kneading step, first, (A) an epoxy resin and (B) a curing agent may be preliminarily mixed, and then other components may be added to perform the kneading. A thermosetting resin composition obtained by premixing using (A) an epoxy resin and (B) a curing agent has improved storage stability and is excellent in moldability during transfer molding.

  In the premixing step, the viscosity of the premix consisting of (A) the epoxy resin and (B) the curing agent is preferably 10 to 10,000 mPa · s at 100 to 150 ° C., and the viscosity at 100 ° C. is 10 to 10,000 mPa · s. More preferably, it is s. When the viscosity is less than 10 mPa · s, burrs are likely to occur during transfer molding. There is a tendency to decrease.

  From the viewpoint of preventing the viscosity of the premix from increasing due to the generation of precipitates in the premixing step, a gel or the like, which is a curing reaction product composed of (A) an epoxy resin and (B) a curing agent, is deposited. It is preferable to prepare the mixing conditions so as not to cause white turbidity in the preliminary mixture due to precipitates. “White turbidity due to precipitates” indicates that there is scattering of electromagnetic waves in the visible light region. More specifically, it indicates that there is no fine particle having a scattering center that causes Rayleigh scattering, Mie scattering, and diffraction scattering phenomenon of light.

  Specifically, in the preliminary mixing step, 100 parts by mass of (A) epoxy and 120 parts by mass of (B) curing agent are weighed in a heat-resistant glass container, and the mixing container is made of a fluid such as silicone oil or water as a medium. The method of heating at 35-180 degreeC can be used using the heater which was made. The heating method is not limited to the above method, and a thermocouple, electromagnetic wave irradiation, or the like can be used, and ultrasonic waves may be irradiated to promote dissolution.

  In the premixing step, (A) epoxy resin and (B) curing agent can be premixed with (A) epoxy resin and (B) a part of curing agent to be blended in the thermosetting resin composition. It is. Specifically, when producing a thermosetting resin composition containing 120 parts by mass of (B) curing agent with respect to 100 parts by mass of (A) epoxy resin, first, 50 parts by mass of (A) epoxy resin and (B) 120 parts by mass of the curing agent is weighed in a container made of heat-resistant glass, and this mixing container is heated at 35 to 180 ° C. using a heater using a fluid such as silicone oil or water as a medium to obtain a preliminary mixture. And even if the obtained preliminary mixture, the remaining (A) 50 mass parts of epoxy resin, (C) white pigment and other components are mixed by the kneader 12 etc., a thermosetting resin composition is manufactured. Good.

(III) Sheet forming step The kneaded thermosetting resin composition extruded from the kneader 12 is formed into a sheet by, for example, being compressed and stretched between two rotating rolls 13 cooled to near room temperature. Is done. Thus, the sheet-like thermosetting resin composition 20 is formed. When the thermosetting resin composition contains an organic acid anhydride having a melting point of 100 ° C. or higher, adhesion of the kneaded material to the surface of the rotating roll can be suppressed in the sheet forming step.

  (III) In the sheet forming step, the thermosetting resin composition formed into a sheet by a rotating roll is air-cooled by a spot cooler or the like on the transport conveyor 14.

(IV) Pulverization process The sheet-formed thermosetting resin composition 20 can be dry-pulverized near room temperature. In this step, the sheet-formed thermosetting resin composition 20 is dry-pulverized. The dry pulverization can be performed using a pulverizer 15 such as a high-speed stirring mill, a Henschel mixer, a power mill, a jet mill, or a roll granulator. These pulverizers 15 can be selectively used depending on the target powder particle size. If the sheet-like thermosetting resin composition 20 does not have a rigidity that can be pulverized at around room temperature (0 to 30 ° C.) (has flexibility), heat is generated due to friction. In some cases, the conductive resin composition adheres in the pulverizing apparatus 15 and processing becomes difficult. According to the thermosetting resin composition of the present invention, adhesion of the thermosetting resin composition into the pulverizing device 15 can be suppressed.

  In addition, in the (IV) pulverization step, it is preferable that a pulverization device 16 is provided at the subsequent stage of the pulverization device 15. Thereby, the powder obtained with the grinding | pulverization apparatus 15 can be further micronized using the micronization apparatus 16, and the moldability of a tablet and the intensity | strength of a tablet can be improved. According to the thermosetting resin composition of the present invention, the adhesion of the powdery thermosetting resin composition 30 to the fine powdering device 16 can also be suppressed, and the powdery thermosetting property from the fine powdering device 16 can be suppressed. Even when the discharge amount of the resin composition 30 is large, clogging of the pulverization apparatus 16 is suppressed.

  In addition, when manufacturing a tablet from the powdery thermosetting resin composition 30 obtained through the pulverization step as described later, when the tablet is continuously automatically formed, the thermosetting property of the powder It is preferable to quantitatively supply the resin composition with a table feeder. When using a table feeder, it is preferable to use a processed powder using a power mill as the grinding device 15. According to the thermosetting resin composition of the present invention, the adhesion of the powdery thermosetting resin composition 30 to the table feeder can also be suppressed.

  As described above, the raw material powder for the tablet can be produced. According to the raw material powder manufacturing method described above, the powder can be continuously manufactured. Thereby, mass production of raw material powder and a tablet is attained.

[Tablet manufacturing method]
The manufacturing method of the tablet which concerns on this embodiment is equipped with the process (tablet process) of pressure-molding the raw material powder of a tablet. A tablet can be produced by pressure-molding the raw material powder of the tablet according to this embodiment. As shown in FIGS. 3 (a) and 3 (b), a raw material powder 24 is filled in a first molding die (mortar-shaped molding die) 21 having a cylindrical hole for filling powder. The raw material powder 24 is formed using cylindrical second molding dies (saddle-shaped molding dies) 22 and 23 that are in close contact with a cylindrical hole of one molding die and have a size that can be taken in and out of the hole. By applying pressure, a thermosetting resin composition 25 molded into a cylindrical shape is obtained. The pressure molding can be performed, for example, at room temperature under a pressing condition of 5 to 50 MPa, 0.1 to 5 seconds, and 0.1 to 10 t.

  After the above pressure molding, the molded thermosetting resin composition 25 is extracted to obtain a tablet 26 as shown in FIG. The thermosetting resin composition 25 molded from the raw material powder composed of the thermosetting resin composition of the present invention is good because it hardly adheres to the surfaces of the first and second molding dies and does not easily crack. A tablet 26 having an appearance can be obtained.

  The thermosetting resin composition of the present invention is useful in various applications such as electrical insulating materials, optical semiconductor sealing materials, adhesive materials, coating materials, and epoxy resin molding materials for transfer molding that require high heat resistance. In particular, the tablet 26 produced by the thermosetting resin composition of the present invention is particularly useful as a material for transfer molding.

[Optical semiconductor device mounting substrate]
The substrate for mounting a semiconductor element of the present invention 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, and at least a part of the wall surface of the recess is the thermosetting resin composition of the present invention. It consists of a cured product. FIG. 4 is a perspective view showing an embodiment of the optical semiconductor element mounting substrate of the present invention. The optical semiconductor element mounting substrate 110 includes a metal wiring 105 on which the Ni / Ag plating 104 is formed and a reflector 103, and a recess formed from the metal wiring 105 on which the Ni / Ag plating 104 is formed and the reflector 103. 200. That is, the bottom surface of the concave portion 200 is composed of the metal wiring 105 on which the Ni / Ag plating 104 is formed, and the wall surface of the concave portion 200 is composed of the reflector 103. The reflector 103 is the thermosetting resin of the present invention. It is a molded article made of a cured product of the composition.

  Although the manufacturing method of the optical semiconductor element mounting substrate of this invention is not specifically limited, For example, it can manufacture by transfer molding using the thermosetting resin composition of this invention. FIG. 5 is a schematic view showing an embodiment of a process for producing an optical semiconductor element mounting substrate of the present invention. The substrate for mounting an optical semiconductor element is formed, for example, by forming a metal wiring 105 from a metal foil by a known method such as punching or etching, and applying Ni / Ag plating 104 by electroplating (FIG. 5A), A step of placing the metal wiring 105 in a mold 151 having a predetermined shape, injecting the thermosetting resin composition of the present invention from the resin injection port 150 of the mold 151, and performing transfer molding under predetermined conditions (FIG. 5B )), And a step of removing the mold 151 (FIG. 5C). In this manner, the optical semiconductor element mounting region (recessed portion) 200 is formed on the optical semiconductor element mounting substrate. The optical semiconductor element mounting region (concave portion) 200 is surrounded by the reflector 103 made of a cured product of the thermosetting resin composition. Preferably, the tablet 26 produced by the thermosetting resin composition of the present invention is preliminarily heated to 30 ° C. to 100 ° C. so as to have a viscosity that can be easily injected into the mold 151. The transfer molding is preferably performed at a mold temperature of 170 to 200 ° C., a molding pressure of 0.5 to 20 MPa for 60 to 120 seconds, and an after cure temperature of 120 to 180 ° C. for 1 to 3 hours.

[Optical semiconductor device]
An optical semiconductor device of the present invention includes the optical semiconductor element mounting substrate, an optical semiconductor element provided in a recess of the optical semiconductor element mounting substrate, and a sealing resin that fills the recess and seals the optical semiconductor element. Part.

  FIG. 6 is a perspective view showing an embodiment in which the optical semiconductor element 100 is mounted on the optical semiconductor element mounting substrate 110 of the present invention. As shown in FIG. 6, the optical semiconductor element 100 is mounted at a predetermined position of the optical semiconductor element mounting region (recessed 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 7 and 8 are schematic cross-sectional views showing an embodiment of the optical semiconductor device of the present invention. As shown in FIGS. 7 and 8, 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. 9 is also a schematic cross-sectional view showing an embodiment of the optical semiconductor device of the present invention. In the optical semiconductor device shown in FIG. 9, the LED element 300 is disposed through 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 body 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.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

<Synthesis Example A1>
[Preparation of polyvalent carboxylic acid condensate]
As a repeating unit monomer, 125 g of hydrogenated terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and as a monomer for both ends, 126 g of hydrogenated 1,2-trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company), After refluxing in acetic anhydride for 5 to 60 minutes under a nitrogen atmosphere, the temperature was raised to 180 ° C., the reaction was carried out in an open system under a nitrogen stream, and the produced acetic acid and water were distilled off. When no volatile components were observed, the reaction vessel was melt-condensed at a temperature of 180 ° C. for 1 to 15 hours while reducing the pressure in the reaction vessel to obtain a polyvalent carboxylic acid condensate.

[Characteristic evaluation of polyvalent carboxylic acid condensate]
The weight average molecular weight, viscosity at 150 ° C., softening point and appearance of the polyvalent carboxylic acid condensate obtained in Synthesis Example A1 were evaluated. The results are shown in Table 1.

The weight average molecular weight was measured using a standard polystyrene calibration curve by gel permeation chromatography (GPC) under the following conditions.
Apparatus: Pump (manufactured by Hitachi, Ltd., trade name: L-6200 type), column (manufactured by Tosoh Corporation, trade name: TSKgel-G5000HXL, TSKgel-G2000HXL), detector (trade name, manufactured by Hitachi, Ltd.) : L-3300RI type)
・ Eluent: Tetrahydrofuran, flow rate 1.0 mL / min ・ Measurement temperature: 30 ° C.

  Viscosity measurements were taken from Research Equipment (London) LTD. This was carried out using an ICI cone plate viscometer made by the manufacturer.

  The softening point was measured using a ring and ball softening point test method in accordance with JISK2207. The appearance was judged visually.

  The polyvalent carboxylic acid condensate obtained in Synthesis Example A1 is very easy to handle for producing a thermosetting resin composition with both a softening point and a viscosity, and the thermosetting resin composition as a part of the curing agent. It can use suitably for a thing.

<Examples 1 to 9 , Reference Examples 10 and 11 , Comparative Examples 1 to 7>
[Preparation of thermosetting resin composition]
According to the mixing ratio (parts by mass) shown in Tables 2 and 3, after premixing (A) epoxy resin and (B) curing agent, the remaining components were added and mixed thoroughly using a mixer, and then mixed with a mixing roll. After melt-kneading under a predetermined condition and cooling, pulverization was performed at 25 ° C., and thermosetting resin compositions of Examples 1 to 9 , Reference Examples 10 and 11, and Comparative Examples 1 to 7 were produced.

[Evaluation of thermosetting resin composition]
(Light reflectivity test)
The obtained thermosetting resin composition was transfer molded under the conditions of molding die temperature: 180 ° C., molding pressure: 6.9 MPa, curing time: 90 seconds, and then post-cured at 150 ° C. for 2 hours to obtain a thickness of 1 A test piece of 0.0 mm was produced. The initial optical reflectivity (light reflectivity) of the test piece at a wavelength of 460 nm was measured using an integrating sphere spectrophotometer V-750 type (trade name, manufactured by JASCO Corporation). The light reflection characteristics were evaluated according to the following evaluation criteria. The results are shown in Tables 2 and 3.
A: Light reflectance of 80% or more at a light wavelength of 460 nm B: Light reflectance of 70% or more and less than 80% at a light wavelength of 460 nm C: Light reflectance of less than 70% at a light wavelength of 460 nm

(Evaluation of properties after kneading)
According to the mixing ratio (parts by mass) shown in Tables 2 and 3, after premixing (A) epoxy resin and (B) curing agent, the remaining components were added and mixed thoroughly using a mixer. Melt kneading was performed using a two-roll mill. It knead | mixed for 15 minutes at 60 degreeC. Properties when the obtained kneaded product was allowed to stand at 25 ° C. for 1 hour were evaluated according to the following evaluation criteria. The results are shown in Tables 2 and 3.
A: Solid, not flexible B: Solid, flexible C: Liquid, fluid

(Evaluation of grindability)
Φ3 (diameter: 3 mm) was selected for the screen mesh, and the thermosetting resin composition produced as described above was pulverized using a pulverizer (product name: P-5, manufactured by Dalton). The thermosetting resin composition was intermittently supplied at a rate of 100 g / min, and the grindability was evaluated. The results are shown in Tables 2 and 3.
A: A good powder is obtained.
B: A component sticking to the apparatus can be seen, but a powder can be obtained without any problem.
C: cannot be pulverized (liquid and too soft to be discharged)

(Evaluation of tabletability)
A tableting machine (manufactured by Powder Machinery Co., Ltd., product name: FK-10) was used, and the first mold having a diameter of the powder filling portion of φ13 mm and a stroke of 60 mm was used. The material was supplied to the first mold so that the tableting pressure was in the range of 0.5 to 3 t and molded at a rate of 6 pieces / min. Based on the following criteria, it was determined whether the tablet after tableting could be molded well and the degree of sticking to the second mold. The results are shown in Tables 2 and 3.

A: A good tablet is obtained.
B: Although a component sticking to the apparatus is seen, a tablet can be obtained without any problem.
C: Tableting is impossible (liquid, too soft to mold).

(Appearance evaluation of tablet)
The appearance of the tablet produced as described above was evaluated based on the following criteria. The results are shown in Tables 2 and 3.

A: There are no cracks or chips.
B: Although micro cracks and chips are seen, the strength is not a problem.
C: Cracks and chips are seen.

* 1: Trisglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd., trade name: TEPIC-S)
* 2: Hexahydrophthalic anhydride (product name: Ricacid HH, manufactured by Shin Nippon Rika Co., Ltd.)
* 3: Methylhexahydrophthalic anhydride (trade name: HN5500, manufactured by Hitachi Chemical Co., Ltd.)
* 4: Succinic anhydride (trade name: Ricacid SA, manufactured by Shin Nippon Rika Kogyo Co., Ltd.)
* 5: Hydrogenated pyromellitic anhydride (trade name: PMDAHS, manufactured by Iwatani Gas Chemical Co., Ltd.)
* 6: Hydrogenated biphenyl dianhydride (trade name: HBPDA, manufactured by Iwatani Gas Chemical Co., Ltd.)
* 7: Tetrahydrophthalic anhydride (Product name: Ricacid TH, manufactured by Shin Nippon Rika Co., Ltd.)
* 8: Hollow particles (manufactured by Sumitomo 3M, trade name: S60-HS)
* 9: Titanium oxide (Ishihara Sangyo Co., Ltd., trade name: CR-63)
* 10: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (Nippon Chemical Industry Co., Ltd., trade name: PX-4ET)
* 11: Trimethoxyepoxysilane (Toray Dow Corning, product name: A-187)
* 12: Fused silica (manufactured by Denki Kagaku Kogyo, trade name: FB-950)
* 13: Fused silica (trade name: S0-25R, manufactured by Denki Kagaku Kogyo Co., Ltd.)

As shown in Tables 2 and 3, the thermosetting resin composition containing the acid anhydride represented by each of the above formulas (1) to (4) as the (B) curing agent is obtained at 25 ° C. after melt-kneading. It was an inflexible solid. And it was able to grind | pulverize without producing adhesion to a grinder. When the obtained powder was molded into a tablet, no adhesion of the powder to the mold was observed, and the tablet did not crack and had a good appearance. Moreover, the cured product of the thermosetting resin composition was excellent in light reflection characteristics. As shown in Comparative Examples 6 and 7, when succinic anhydride does not contain (C) a white pigment, discoloration of the cured product is remarkable. However, as shown in Examples 1 and 2 and Reference Example 10 , when hollow particles and titanium oxide were used as the white pigment (C), it was found that the cured product did not change color.

DESCRIPTION OF SYMBOLS 10 ... Raw material powder manufacturing apparatus, 11 ... Raw material supply part, 12 ... Kneading machine, 13 ... Rotary roll, 14 ... Conveyor, 15 ... Grinding device, 16 ... Fine powdering apparatus, 20 ... Sheet-like thermosetting resin composition , 13, 24 ... powdered thermosetting resin composition, 21 ... first molding die, 22, 23 ... second molding die, 25 ... thermosetting resin composition during pressure molding, 26 ... Tablet: 100: optical semiconductor element, 101: transparent sealing resin, 102: bonding wire, 103: cured product of thermosetting resin composition (reflector), 104: Ni / Ag plating, 105: metal wiring, 106: fluorescence , 107 ... solder bump, 110 ... substrate for mounting optical semiconductor element, 200 ... mounting area for optical semiconductor element, 150 ... resin injection port, 151 ... mold, 300 ... LED element, 301 ... bonding wire, 302 ... Akirafutome resin, 303 ... Reflector 304 ... lead, 305 ... phosphor, 306 ... die bonding material.

Claims (8)

(A) an epoxy resin (B) a thermosetting resin composition containing a curing agent and (C) a white pigment,
The (B) curing agent includes an organic acid anhydride having a melting point of 100 ° C. or higher, and a polyvalent carboxylic acid condensate,
Wherein (C) white pigment, alumina, magnesium oxide, looking contains at least one inorganic antimony oxide, titanium oxide, selected from the group consisting of zirconium oxide and inorganic hollow particles,
A thermosetting resin composition for light reflection used in transfer molding, wherein the inorganic hollow particles are at least one selected from the group consisting of sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, and shirasu (white sand) .   The thermosetting resin composition for light reflection according to claim 1, wherein the organic acid anhydride is a non-aromatic compound.   The thermosetting resin composition for light reflection according to claim 1 or 2, wherein the organic acid anhydride has a Hazen color number of 50 or less. The organic acid anhydride contains at least one acid anhydride selected from the group consisting of compounds represented by the following formulas (1), (2), (3), and (4), respectively. The thermosetting resin composition for light reflection as described in any one of -3.

  The light-reflective thermosetting resin according to any one of claims 1 to 4, wherein the content of the organic acid anhydride is 3 to 100% by mass based on the mass of the (B) curing agent. Composition. Having a recess composed of a bottom surface and a wall surface;
The optical semiconductor element which the bottom face of the said recessed part is an optical semiconductor element mounting part, and at least one part of the wall surface of the said recessed part consists of hardened | cured material of the thermosetting resin composition as described in any one of Claims 1-5. Mounting board. A method of manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface,
The manufacturing method of the board | substrate for optical semiconductor element mounting provided with the process of forming at least one part of the wall surface of the said recessed part using the thermosetting resin composition as described in any one of Claims 1-5. An optical semiconductor element mounting substrate having a recess composed of a bottom surface and a wall surface;
An optical semiconductor element provided in a recess of the optical semiconductor element mounting substrate;
A sealing resin portion that fills the recess and seals the optical semiconductor element;
With
The optical semiconductor device in which at least one part of the wall surface of the said recessed part consists of hardened | cured material of the thermosetting resin composition as described in any one of Claims 1-5.

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