JP2013079384A - Substrate for mounting optical semiconductor element, method for producing the same, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for mounting an optical semiconductor element, which uses a thermosetting resin composition enabling a simplified molding process, a method for producing the same, and an optical semiconductor device.SOLUTION: The substrate for mounting an optical semiconductor element includes a resin molding which includes a recessed portion composed of a bottom surface and an inner peripheral side, and also forms the inner peripheral side, wherein the bottom surface is a region for mounting an optical semiconductor element. The resin molding is formed from a thermosetting resin composition containing an epoxy resin and a curing agent. The cured product, which is obtained by performing transfer molding of the thermosetting resin composition on the condition that mold temperature is 180°C and curing time is 90 seconds, has a cure degree substantially equivalent to that of the cured product further experienced after curing by being heated at 150°C for three hours.

Description

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

  Conventionally, epoxy resins have various characteristics such as electrical insulation materials, semiconductor device materials, optical semiconductor sealing materials, adhesive materials and paint materials, taking advantage of the characteristics such as excellent electrical insulation, mechanical strength, adhesion and water resistance. It is used for various purposes.

  In general, an optical semiconductor device is configured by combining an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor. Since the optical semiconductor device has advantages such as high energy efficiency and long life, the demand for the display for outdoor use, portable liquid crystal backlight, in-vehicle use and the like has been increasing in recent years. An optical semiconductor element mounting substrate used in an optical semiconductor device is mainly manufactured by an injection molding method. For example, by using a thermoplastic resin composition in which a thermoplastic resin and a white pigment such as titanium dioxide are combined, a substrate for mounting an optical semiconductor element is provided that is inexpensive and excellent in productivity by taking advantage of the characteristics of an injection molding method. .

  Patent Document 1 discloses a substrate for mounting an optical semiconductor element using a thermosetting resin containing an epoxy resin and an acid anhydride curing agent.

JP 2006-140207 A

  Although conventional thermosetting resin compositions are superior in durability to thermoplastic resin molding materials used in injection molding and extrusion molding methods, they require many steps and are disadvantageous in terms of productivity. It was a thing.

  Then, the objective of this invention is providing the thermosetting resin composition which enables the simplification of the process of shaping | molding. Moreover, an object of this invention is to provide the optical semiconductor device using the said resin composition, and its manufacturing method.

  The present invention relates to a thermosetting resin composition containing an epoxy resin, a curing agent and a curing catalyst. The degree of cure of the cured product obtained by transfer molding of the thermosetting resin composition according to the present invention under conditions of a mold temperature of 180 ° C. and a curing time of 90 seconds was further cured by heating at 150 ° C. for 3 hours. Substantially equivalent to the later cured product.

  The glass transition temperature, the storage elastic modulus at 40 ° C., and the linear expansion in the glass region of a cured product obtained by transfer molding of the thermosetting resin composition according to the present invention under conditions of a mold temperature of 180 ° C. and a curing time of 90 seconds. At least one of the coefficients may be within a range of −5% to + 5% with respect to the cured product after further being cured by heating at 150 ° C. for 3 hours.

  According to the thermosetting resin composition of the present invention, the degree of cure, the glass transition temperature, the storage elastic modulus, or the linear expansion coefficient substantially the same as that after the after-curing is achieved even before the after-curing. Is done. Therefore, it is possible to produce a molded article of the thermosetting resin composition without performing an after-curing step. As a result, the process can be greatly simplified in the molding of the thermosetting resin composition.

  The thermosetting resin composition having the above-described characteristics can be obtained, for example, by using a curing agent containing a polyvalent carboxylic acid condensate represented by the following general formula (1). Furthermore, by using such a curing agent, a transparent and less colored cured product can be obtained from the thermosetting resin composition.

  In the formula (1), Rx represents an aliphatic hydrocarbon ring and the aliphatic hydrocarbon ring represents a divalent group which may be substituted with a halogen atom or a linear or branched hydrocarbon group, A plurality of Rx in the same molecule may be the same or different, and Ry represents a monovalent hydrocarbon group which may be substituted with an acid anhydride group or a carboxylic ester group, and two Rx in the same molecule Ry may be the same or different, and n1 represents an integer of 1 or more.

  Ry is selected from a monovalent group represented by the following chemical formula (20), or cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene, and hydrogenated biphenyl. It is preferably a monovalent group derived by removing a hydrogen atom from the cycloaliphatic hydrocarbon.

The polyvalent carboxylic acid condensate represented by the general formula (1) is particularly preferably a compound represented by the following general formula (1a). In the formula (1a), m represents an integer of 0 to 4, Rz represents a halogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and when m is 2 to 4, a plurality of Rz may be the same or different and may be linked to each other to form a ring, and n1 represents an integer of 1 or more.

The curing agent is a polyvalent carboxylic acid condensation obtainable by a method of condensing a tricarboxylic acid compound represented by the following general formula (21) and a monocarboxylic acid compound represented by the following general formula (22) between molecules. May contain body. By using such a curing agent, even before the after cure, substantially the same degree of cure, glass transition temperature, storage elastic modulus, or linear expansion coefficient as after the after cure can be achieved.

In formulas (21) and (22), R ¹ represents a trivalent group having an aliphatic hydrocarbon ring, a non-aromatic heterocyclic ring or a siloxane ring, and R ² is substituted with an acid anhydride group or a carboxylic ester group. 1 represents a monovalent hydrocarbon group, and two R ² in the same molecule may be the same or different.

The tricarboxylic acid compound may be an isocyanuric acid derivative represented by the following general formula (21a), and the monocarboxylic acid compound may be a hydrogenated trimellitic acid anhydride represented by the following chemical formula (22a). In formula (21a), R ³ represents a saturated hydrocarbon group or an unsaturated hydrocarbon group.

  The curing agent may further contain a polyvalent carboxylic acid condensate represented by the following chemical formula (3).

  The content of the curing catalyst is preferably in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and the curing agent.

  In another aspect, the present invention includes an optical semiconductor element mounting having a resin molded product that has a recess composed of a bottom surface and an inner peripheral side surface and forms the inner peripheral side surface, and the bottom surface is an optical semiconductor element mounting region. Related to the substrate The resin molded product can be formed from the thermosetting resin composition according to the present invention.

  The substrate for mounting an optical semiconductor element according to the present invention can be manufactured with high productivity by a simplified process. Further, the optical semiconductor element mounting substrate according to the present invention is sufficiently excellent in terms of durability.

  In still another aspect, the present invention provides an optical semiconductor element having a recess formed of a bottom surface and an inner peripheral side surface and a resin molded product forming the inner peripheral side surface, the bottom surface being an optical semiconductor element mounting region The present invention relates to a method for manufacturing a mounting substrate. The manufacturing method according to the present invention includes a step of forming the resin molded product by transfer molding the thermosetting resin composition according to the present invention.

  According to the manufacturing method of the present invention, it is possible to manufacture an optical semiconductor element mounting substrate having excellent durability with high productivity.

  In still another aspect, the present invention relates to an optical semiconductor device. An optical semiconductor device according to the present invention includes an optical semiconductor element mounting substrate according to the present invention, an optical semiconductor element mounted in an optical semiconductor element mounting region of the optical semiconductor element mounting substrate, and the optical semiconductor element in the optical semiconductor device. And a sealing resin layer that covers the concave portion of the semiconductor element mounting substrate.

  The optical semiconductor device according to the present invention can be manufactured with high productivity by a simplified process. In addition, the optical semiconductor device according to the present invention is sufficiently excellent in terms of durability.

  According to the present invention, there is provided a thermosetting resin composition capable of simplifying the molding process. When molding the thermosetting resin composition according to the present invention, the after-curing step can be omitted, and the equipment required for after-curing is not required.

  The thermosetting resin composition according to the present invention is excellent in terms of heat resistance and light resistance, and is used for forming a resin molded product used as a light reflecting member (reflector) constituting a substrate for mounting an optical semiconductor device. It is particularly useful as a thermosetting resin composition. Particularly in recent years, the brightness of LED devices has increased, and the problem of deterioration of materials due to an increase in the junction temperature due to an increase in the amount of heat generated by the elements and a direct increase in light energy has become apparent. It is important to have excellent properties.

It is a perspective view which shows one Embodiment of an optical semiconductor device. It is sectional drawing which follows the II-II line | wire of FIG. It is sectional drawing which shows one Embodiment of an optical semiconductor device. It is sectional drawing which shows one Embodiment of an optical semiconductor device.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The thermosetting resin composition according to this embodiment contains an epoxy resin, a curing agent, and a curing catalyst. The thermosetting resin composition of the present invention according to the present embodiment is particularly suitably used as a light reflecting thermosetting resin composition used to form a resin molded product as a light reflecting member of an optical semiconductor device or the like. It is done.

  A cured product obtained by transfer molding of the thermosetting resin composition according to the present embodiment under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds is further heated by heating at 150 ° C. for 3 hours. When after-curing, the degree of cure of the cured product before after-curing is substantially equivalent to the degree of curing of the cured product after after-curing. In other words, the cured product before after-curing has a glass transition temperature substantially equal to that of the cured product after after-curing, a storage elastic modulus at 40 ° C., or a linear expansion coefficient in the glass region. More specifically, at least one of the glass transition temperature, the storage elastic modulus at 40 ° C., and the linear expansion coefficient in the glass region of the cured product obtained by transfer molding is obtained by heating at 150 ° C. for 3 hours. Furthermore, it is within ± 5% with respect to the cured product after being cured.

  If the change in physical properties such as glass transition temperature is greater than ± 5%, after-curing is required to obtain a fully cured molded product, which is disadvantageous in terms of manufacturing man-hours and time. . When proceeding to the subsequent manufacturing process without sufficiently proceeding with the curing reaction, for example, a step of adhering the optical semiconductor element or a step of mounting the optical semiconductor device to a printed circuit board by soldering, high-temperature reflow, etc. In a process under a high temperature condition that requires heating, there is a risk that the package or lead frame may be peeled off and cracked, or the thermosetting resin itself may be deteriorated due to thermal decomposition. For this reason, it may be difficult to manufacture the optical semiconductor device.

  The storage elastic modulus was measured, for example, by measuring the dynamic viscoelasticity of a test piece cut out from a cured product (resin molded product) before and after after-curing under conditions of a torsion mode and a heating rate of 5 ° C./min. It can measure by the method of reading the storage elastic modulus in predetermined | prescribed temperature (for example, 40 degreeC) from dynamic viscoelasticity. As the measuring device, for example, ARES2KSTD manufactured by TA Instruments (formerly Rheometric) is used.

  The glass transition temperature and the linear expansion coefficient are, for example, a linear expansion curve of a test piece having a size of 19 mm × 3 mm × 3 mm cut out from each cured product before and after after-curing under the condition of a heating rate of 5 ° C./min. It is measured by the measuring method. The glass transition temperature is determined based on the inflection point of the linear expansion coefficient. Furthermore, the linear expansion coefficient at a predetermined temperature in the temperature region (glass region) below the glass transition temperature is read from the linear expansion curve. Usually, the linear expansion coefficient at 40 ° C. is the linear expansion coefficient in the glass region. The linear expansion curve is measured using, for example, a TASS6000 manufactured by Seiko Instruments Inc.

  The thermosetting resin composition can be molded by a molding method involving thermosetting to produce a resin molded product. The curing conditions are not particularly limited. Examples of the molding method include methods such as transfer molding, compression molding, and cast molding. The molding of the semiconductor sealing resin, the optical semiconductor sealing resin, and the resin for the optical semiconductor element mounting substrate is performed, for example, by transfer molding with a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Even with such a short-time curing, according to the thermosetting resin composition according to the present embodiment, it is possible to achieve a sufficient degree of curing, the conventionally required after cure process Can be omitted.

  The thermosetting resin composition contains one or more epoxy resins. As an epoxy resin, what is generally used, for example as an epoxy resin molding material for electronic component sealing can be used. Specific examples of the epoxy resin include epoxidized phenol and aldehyde novolak resins such as phenol novolak type epoxy resin and orthocresol novolak type epoxy resin, bisphenol A, bisphenol F, bisphenol S and alkyl-substituted bisphenol. Diglycidyl ether such as diglycidyl ether, diaminodiphenylmethane and isocyanuric acid, etc., glycidylamine epoxy resin obtained by reaction of epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, and fat There are cyclic epoxy resins. Of these, those which are relatively uncolored are preferred. From such a viewpoint, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate, and 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or At least one epoxy resin selected from dicarboxylic acid diglycidyl esters derived from 1,4-cyclohexanedicarboxylic acid is preferred. 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 preferred. Also preferred are glycidyl esters of nuclear hydrogenated trimellitic acid or nuclear hydrogenated pyromellitic acid. Furthermore, the polyorganosiloxane which has an epoxy group manufactured by heating a silane compound in presence of an organic solvent, an organic base, and water, and making it hydrolyze and condense is also preferable. An epoxy resin represented by the following formula (7), which is a copolymer of a glycidyl methacrylate monomer and a polymerizable monomer, can also be used.

In formula (7), R ⁵ represents a glycidyl group, R ⁶ and R ⁷ each independently represent a hydrogen atom or a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁸ represents 1 Represents a saturated saturated hydrocarbon group. a and b represent a positive integer.

  In order to achieve the above-described curing characteristics, the thermosetting resin composition includes a polyvalent carboxylic acid condensate represented by a polyvalent carboxylic acid condensate represented by the following general formula (1). It is preferable.

  Rx in the formula (1) is a divalent saturated hydrocarbon group having a saturated hydrocarbon ring. When Rx 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 Rx in the same molecule may be the same or different. The saturated hydrocarbon ring of Rx 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. The number of carbon atoms in Rx is preferably 3-15.

  Rx is a group derived by removing a carboxyl group from a polyvalent carboxylic acid as a monomer used to obtain the polymer of the formula (1). The polyvalent carboxylic acid as a monomer preferably has a boiling point higher than the reaction temperature of polycondensation.

  More specifically, Rx is a hydrogen atom from a cyclic aliphatic hydrocarbon selected from cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated hydronaphthalene and hydrogenated biphenyl. It is preferably a divalent group derived by removing. When Rx is such a group, 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, Rx 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, Rx is preferably a divalent group represented by the following general formula (10). In formula (10), m represents an integer of 0 to 4. Rz 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 Rz may be the same or different, and may be connected to each other to form a ring.

  Ry which is a terminal group in the formula (1) represents a monovalent hydrocarbon group which may be substituted with an acid anhydride group or a carboxylic ester group. Two Ry may be the same or different. Ry may be a monovalent group derived by removing a carboxyl group from a linear, branched or cyclic C2-C15 aliphatic or aromatic monocarboxylic acid (such as benzoic acid). . The terminal carboxyl group is blocked by Ry, thereby reducing the carboxylic acid group concentration when the curing agent is synthesized. As a result, dispersion of the molecular weight of the polyvalent carboxylic acid condensate of formula (1) can be suppressed.

  Ry is preferably a monovalent group represented by the following chemical formula (20), or cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene and hydrogenated It is a monovalent group derived by removing a hydrogen atom from a cycloaliphatic hydrocarbon selected from biphenyl. When Ry is any of these groups, the effect of obtaining a cured product that is transparent and less colored by heat is more remarkably exhibited.

  Rx may be a divalent group represented by the general formula (10), and at the same time, Ry may be a monovalent group represented by the chemical formula (20). That is, the polycarboxylic acid condensate of formula (1) may be a compound represented by the following general formula (1a).

  N1 of Formula (1) and (1a) shows an integer greater than or equal to 1, Preferably it is an integer of 1-200.

  In the reaction liquid containing the polycarboxylic acid represented by the following general formula (5) and the monocarboxylic acid represented by the following general formula (6), for example, the polyvalent carboxylic acid condensate of the formula (1) It can be obtained by a method comprising a step of dehydrating and condensing the carboxyl groups each has between molecules.

  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 30 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 1 hour 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.

  The curing agent is a polyvalent carboxylic acid condensation obtainable by a method of condensing a tricarboxylic acid compound represented by the following general formula (21) and a monocarboxylic acid compound represented by the following general formula (22) between molecules. (Hereinafter sometimes referred to as “tricarboxylic acid condensate”). This tricarboxylic acid condensate can be used alone or in combination with the polycarboxylic acid condensate of the formula (1).

  The tricarboxylic acid condensate contains a compound represented by the following general formula (2) as a main component.

In the formulas (21), (22) and (2), R ¹ represents a trivalent group having an aliphatic hydrocarbon ring, a non-aromatic heterocyclic ring or a siloxane ring, and R ² represents an acid anhydride group or a carboxylic acid A monovalent hydrocarbon group which may be substituted with an ester group is shown.

R ¹ is a non-aromatic heterocyclic ring such as an aliphatic hydrocarbon ring selected from cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene, hydrogenated biphenyl, and cyclic siloxane, isocyanuric ring, Or it has a siloxane ring. Thereby, a transparent cured product can be obtained.

The monocarboxylic acid compound of formula (22) preferably has a boiling point higher than the temperature of the condensation reaction. Monocarboxylic acid compounds of formula (22) are, for example, hydrogenated trimellitic anhydride, or cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene and hydrogen Selected from monocarboxylic acids derived from biphenyl fluoride and derivatives thereof. R ² is a group derived from these monocarboxylic acid compounds by removing a carboxyl group. Among these monocarboxylic acid compounds, monocarboxylic acids in which a carboxyl group is bonded to cyclohexane and its derivatives are desirable from the viewpoint of being inexpensive.

  The tricarboxylic acid compound of the formula (21) is preferably an isocyanuric acid derivative represented by the following general formula (21a). Further, the monocarboxylic acid compound of the formula (22) is preferably a hydrogenated trimellitic anhydride represented by the following chemical formula (22a). Preferably, the tricarboxylic acid condensate includes a compound represented by the following general formula (2a).

In the formulas (21a) and (2a), R ³ represents a saturated hydrocarbon group or an unsaturated hydrocarbon group. R ³ is preferably a linear, branched, alicyclic or heterocyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 2 to 15 carbon atoms.

  The tricarboxylic acid compound of the formula (21) and the monocarboxylic acid compound of the formula (22) are preferably reacted at a ratio of 3 equivalents to 1 equivalent of tricarboxylic acid.

  The curing agent may further contain a polyvalent carboxylic acid condensate represented by the following chemical formula (3). The polyvalent carboxylic acid condensate of formula (3) is derived from two hydrogenated trimellitic anhydride molecules. The compound of the formula (3) may be generated as a by-product when the polyvalent carboxylic acid condensate of the formula (1) or the tricarboxylic acid condensate is produced.

  The number average molecular weight Mn of the polycarboxylic acid condensate of the formula (1) and the tricarboxylic acid condensate is preferably 200 to 20000. When the number average molecular weight Mn is smaller than 200, there is a tendency that the occurrence of resin contamination increases when the thermosetting resin composition is transfer molded. When the number average molecular weight Mn is larger than 20000, the compatibility of the polyvalent carboxylic acid condensate with the epoxy resin tends to decrease, and the fluidity during transfer molding of the thermosetting fat composition tends to decrease. .

  The number average molecular weight Mn of the polyvalent carboxylic acid condensate is a conversion value measured by gel permeation chromatography (GPC) based on a calibration curve with standard polystyrene. GPC includes, for example, a pump (L-6200 manufactured by Hitachi, Ltd.), a column (TSKgel-G5000HXL and TSKgel-G2000HXL, both of which are trade names manufactured by Tosoh Corporation) and a detector (L-3300RI type manufactured by Hitachi, Ltd.). ) Using tetrahydrofuran as an eluent, under the conditions of a temperature of 30 ° C. and a flow rate of 1.0 ml / min.

  The viscosity of the polycarboxylic acid condensate of the formula (1) and the tricarboxylic acid condensate as measured with an ICI cone plate viscometer is preferably 100 to 30000 mPa · s in the range of 100 to 150 ° C. . When this viscosity is less than 100 mPa · s, there is a tendency that the occurrence of resin contamination increases when transfer molding the thermosetting resin composition. Moreover, when a viscosity is larger than 30000 mPa * s, there exists a tendency for the fluidity | liquidity in the metal mold | die at the time of transfer molding of a thermosetting resin composition to fall. Here, “viscosity” indicates the viscosity when measured using an ICI cone plate viscometer. The viscosity of the polyvalent carboxylic acid condensate can be measured, for example, by Research Equipment (London) LTD. It can be measured using a manufactured ICI cone plate viscometer.

  The softening point of the polycarboxylic acid condensate of formula (1) and the tricarboxylic acid condensate is preferably 20 to 150 ° C. When the softening point is less than 20 ° C., the handling property, kneading property and dispersibility in producing the thermosetting resin composition are lowered, and it tends to be difficult to obtain a uniform composition. Moreover, if the softening point is low, it tends to be difficult to effectively suppress the occurrence of resin stains during transfer molding. When the softening point is higher than 150 ° C., when the thermosetting resin composition is heated to 100 ° C. to 200 ° C. for transfer molding, compression molding or cast molding, the solid matter remains in the resin composition. there is a possibility. As a result, there is a possibility that a uniform molded product (cured body) cannot be obtained. The softening point of the polyvalent carboxylic acid condensate is more preferably 30 to 80 ° C, still more preferably 30 to 50 ° C. Thereby, the kneadability at the time of manufacturing a thermosetting resin composition improves more.

  The thermosetting resin composition may further contain a compound other than the polyvalent carboxylic acid condensate as described above as a curing agent. As other curing agents, for example, those generally used in epoxy resin molding materials for electronic component sealing can be used. The other curing agent is preferably an acid anhydride curing agent (excluding the above-mentioned polyvalent carboxylic acid condensate) or an isocyanuric acid derivative. An acid anhydride curing agent is a compound formed by ring-closing condensation of a polyvalent carboxylic acid in a molecule.

  Acid anhydride curing agents include, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride Dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, and methyl tetrahydrophthalic anhydride. Isocyanuric acid derivatives include, for example, 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxyl). Propyl) isocyanurate and 1,3-bis (2-carboxyethyl) isocyanurate. 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, diethyl anhydride Glutaric acid and 1,3,5-tris (3-carboxypropyl) isocyanurate are preferred.

  The curing agent other than the polyvalent carboxylic acid condensate preferably has a molecular weight of 100 to 10,000, and is preferably colorless or light yellow. An acid anhydride having an aromatic ring such as trimellitic anhydride and pyromellitic anhydride is preferably used as a hydride obtained by hydrogenating all unsaturated bonds of the aromatic ring. You may use the acid anhydride generally used as a raw material of a polyimide resin.

  The thermosetting resin composition preferably contains 100 parts by weight of an epoxy resin and 1 to 150 parts by weight of a curing agent. From the viewpoint of suppressing resin contamination during molding, the curing agent is more preferably 50 to 120 parts by weight with respect to 100 parts by weight of the epoxy resin.

  The epoxy resin and the curing agent are preferably 0.6 to 2 active groups (an acid anhydride group and a hydroxyl group) in the curing agent capable of reacting with the epoxy group with respect to 1 equivalent of the epoxy group in the epoxy resin. It is mix | blended so that it may become 0.0 equivalent, More preferably, it is 0.7-0.8 equivalent. There exists a tendency for the cure rate of a thermosetting resin composition to fall that the equivalent of an active group is less than 0.6, and for the glass transition temperature and elastic modulus of the hardened | cured material obtained to fall. On the other hand, when the active group exceeds 2.0 equivalents, the strength of the cured product may decrease.

  Curing catalysts include, for example, tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine and tri-2,4,6-dimethylaminomethylphenol; Imidazoles such as 4-methylimidazole and 2-methylimidazole; triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoro Phosphorus compounds such as borates, tetra-n-butylphosphonium-tetraphenylborate, tetra-n-butyldimethylphosphate, tetra-n-butylphosphonium acetate and tetra-n-butylphosphonium octylcarboxylate; Salts; and derivatives thereof. These may be used alone or in combination. Among these curing catalysts, tertiary amines, imidazoles or phosphorus compounds are preferably used.

  The content of the curing catalyst is preferably in the range of 1 to 5 parts by weight, more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the total total weight of the epoxy resin and (B) curing agent. When the content of the curing accelerator is less than 1 part by weight, the curing acceleration effect tends to be small, and when it exceeds 5 parts by weight, discoloration may be seen in the resulting molded article.

  The thermosetting resin composition preferably further contains at least one of an organic acid metal salt and a metal alkoxide in addition to the epoxy resin, the curing agent, and the curing accelerator. These can function as curing aids that further activate the curing catalyst.

The organic acid metal salt has the following general formula (8):
(R0-COO) qM1
It is preferable that it is a metal soap represented by these. In Formula (8), R0 is an alkylene group, an alkyl group, an aryl group, an alkoxy group, a monovalent organic group having 3 to 50 carbon atoms having an epoxy group, a monovalent organic group having a carboxyl group, or 3 to 3 carbon atoms. 500 represents a polyalkylene ether group, M1 represents a metal element belonging to the third period, Group IIA, IVB, IIB, Group VIII, Group IB, Group IIIA, IIIB or IVA, and q represents 1 Represents an integer of ~ 4.

  M1 is preferably selected from magnesium, calcium, barium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc. From the viewpoint of chemical or physical stability, aluminum, tin, titanium, iron, cobalt, nickel, copper, or zinc is more preferable. Zinc is most preferred. In a process involving a chemical reaction such as a thermosetting reaction process of a thermosetting resin composition or B-stage formation (oligomerization or high molecular weight) at the time of kneading, a metal compound contained in the metal soap causes an unexpected side reaction. It is preferable to appropriately select an organic acid metal salt that does not act as a reaction catalyst.

  R0 is a group obtained by removing a carboxyl group from a monovalent aliphatic carboxylic acid having 10 to 50 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, and montanic acid.

  Specific examples of the organic acid metal salt include aluminum stearate and zinc stearate. Examples of commercially available products include zinc stearate and aluminum stearate 300 manufactured by Nippon Oil & Fat Co., Ltd.

  As the organic acid metal salt, a metal soap produced by a wet method using an alkali metal salt aqueous solution of an organic acid and an M1 metal salt or a dry method in which a fatty acid and an M1 metal are directly reacted is known. Such metal soaps may contain free fatty acids and moisture. At room temperature (0 to 35 ° C.), the content of free fatty acid in the metal soap is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, and particularly preferably 0.5% or less. % By weight or less. When there is more content of free fatty acid than 20 weight%, the storage stability of a thermosetting resin composition may fall. At room temperature (0 to 35 ° C.), the water content in the metal soap is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, and particularly preferably 0.5% by weight. % Or less. If the water content in the metal soap is more than 10% by weight, the reflow resistance of the molded article after curing may be lowered.

  The organic acid metal salt preferably has a melting point of 100 ° C. or higher and lower than 200 ° C. from the viewpoint of dispersibility with respect to the epoxy resin and the curing agent. The melting point of the organic acid metal salt is more preferably 100 ° C. or higher and lower than 150 ° C., particularly preferably 110 ° C. or higher and lower than 135 ° C. When the melting point exceeds 200 ° C., the dispersibility is lowered, and the organic acid metal salt tends to be unevenly distributed in the thermosetting resin composition in the molding step. As a result, a mold release failure may occur. When the melting point is less than 100 ° C., the kneadability may not be sufficiently ensured because the viscosity of the thermosetting resin composition is lowered during kneading by a mixing roll mill or biaxial extrusion.

  The metal alkoxide is a compound in which the same number of organic alkoxide molecules as the valence is bonded to a metal atom, or a compound in which these are quantified to form a chain. The metal alkoxide is not particularly limited, but is preferably at least one selected from silane alkoxide, aluminum alkoxide and titanium alkoxide. Among these, silane alkoxide is preferable from the viewpoint of material cost. The organic alkoxide is not particularly limited, but is preferably an alkyl oxide having 2 to 10 carbon atoms (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, etc.). Of these, tetraethoxysilane is particularly preferable. For example, tetramethoxysilane is highly reactive and easily gels when moisture is mixed therein. Tetraethoxysilane is preferable to tetramethoxysilane from the viewpoint of preventing aggregation of the white pigment.

  The content of the metal alkoxide is preferably 0.5 to 20 parts by weight, more preferably 1.0 to 10 parts by weight with respect to 100 parts by weight of the epoxy. When this content is larger than 20 parts by weight, the white pigment tends to aggregate and the curability of the thermosetting resin composition tends to decrease. When the content is less than 0.5 parts by weight, the curing acceleration effect as a curing aid tends to decrease.

  The thermosetting resin composition preferably contains a white pigment in order to achieve high reflectance. A well-known thing can be especially used for a white pigment without a restriction | limiting. The white pigment is, for example, at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu. The white pigment may be inorganic hollow particles. The inorganic hollow particles include, for example, sodium silicate glass, aluminum silicate glass, borosilicate soda glass, or shirasu. The center particle diameter of the white pigment is preferably in the range of 0.1 to 50 μm. When the center particle size is less than 0.1 μm, the particles tend to aggregate, so that the dispersibility tends to be lowered. When the center particle size exceeds 50 μm, the reflection property of the cured product may be lowered.

  The thermosetting resin composition may further contain an inorganic filler other than the white pigment. The moldability can be adjusted by blending the inorganic filler. The inorganic filler is not particularly limited, but is at least one selected from the group consisting of silica, antimony oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. Two or more combinations selected from silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, and magnesium hydroxide from the viewpoints of thermal conductivity, light reflection characteristics, moldability, and flame retardancy Is preferred.

  The center particle diameter of the inorganic filler is not particularly limited, but is preferably in the range of 1 to 100 μm so that packing with the white pigment is efficient.

  The total amount of the inorganic filler and the white pigment is preferably in the range of 10% by volume to 85% by volume with respect to the entire thermosetting resin composition. If this amount is less than 10% by volume, There exists a tendency for a light reflection characteristic to fall, and when it exceeds 85 volume%, there exists a tendency for the moldability of a resin composition to fall.

  It is preferable that a thermosetting resin composition contains a coupling agent from a viewpoint of improving the adhesiveness of an epoxy resin and a hardening | curing agent, an inorganic filler, and a white pigment. Although it does not specifically limit as a coupling agent, For example, there exist a silane coupling agent, a titanate coupling agent, etc. Examples of the silane coupling agent include epoxy silane, amino silane, cationic silane, vinyl silane, acrylic silane, mercapto silane, and combinations thereof. Often used in any amount of deposit. The amount, type and processing conditions of the coupling agent are not particularly limited. The blending amount of the coupling agent is preferably 5% by weight or less with respect to the entire thermosetting resin composition. The thermosetting resin composition may contain additives such as an antioxidant, a release agent, and an ion scavenger as necessary.

  It is preferable that the thermosetting resin composition before thermosetting can form a tablet at room temperature (15-30 degreeC) by pressure molding. For example, the pressure molding may be performed at room temperature (25 ° C.) under conditions of 5 to 50 MPa and about 1 to 5 seconds.

  The light reflectance of the cured product formed by thermal curing of the thermosetting resin composition is desirably 80% or more at a wavelength of 350 nm to 800 nm. If the light reflectance is less than 80%, the effect of improving the luminance of the optical semiconductor device tends to be reduced. More preferably, the light reflectance is 90% or more.

  The thermosetting resin composition can be obtained by a method in which the various components are uniformly dispersed and mixed. The mixing means and conditions are not particularly limited. As a general method, a method of (melting) kneading with an extruder, a kneader, a roll, an extruder or the like, and cooling and pulverizing the kneaded product can be mentioned. The conditions for (melting) kneading may be appropriately determined depending on the types and blending amounts of the components, and are not particularly limited, but are preferably (melting) kneading in the range of 15 ° C. to 100 ° C. for 5 to 40 minutes, It is more preferable to knead (melt) for 10 to 30 minutes in the range of 100 ° C. When the (melting) kneading temperature is less than 15 ° C., it is difficult to (melt) kneading each component, and the dispersibility tends to decrease. When the temperature is higher than 100 ° C., the resin composition has a high temperature. There is a possibility that the molecular weight proceeds and the resin composition is cured. Further, when the (melting) kneading time is less than 5 minutes, there is a high possibility that resin stains (resin burrs) are generated during transfer molding. If resin contamination occurs in the opening of the optical semiconductor element mounting region, it may become an obstacle when mounting the optical semiconductor element, or when the optical semiconductor element and the metal wiring are electrically connected by a method such as a bonding wire. Can be an obstacle. If the kneading time is longer than 30 minutes, the resin composition may increase in molecular weight and the resin composition may be cured.

  You may manufacture a thermosetting resin composition by the method of knead | mixing a mixture using a roll mill, an extruder, etc., after pre-mixing an epoxy resin and a hardening | curing agent as needed. When at least one of the epoxy resin and the curing agent is liquid in a temperature range of 0 ° C. to 35 ° C. or has a low viscosity of less than 10 mPa · s in a temperature range of 100 to 200 ° C., premixing It is preferable to implement. If pre-mixing is not performed in such a case, the storage stability of the thermosetting resin composition tends to decrease, or the melt viscosity tends to be extremely low, making transfer molding difficult.

  In the step of premixing the epoxy resin and the curing agent in advance, the viscosity of the mixture is preferably in the range of 10 to 10000 mPa · s in the range of 100 to 150 ° C., and the viscosity at 100 ° C. is in the range of 10 to 10000 mPa -More preferably in the range of s. If this viscosity is lower than 10 mPa · s, burrs tend to occur during transfer molding, and if it exceeds 10000 mPa · s, the fluidity decreases, making it difficult to mold by pouring a resin into the mold. Tend.

  It is preferable that the epoxy resin and the curing agent have compatibility. In other words, it is preferable that the epoxy resins and the epoxy resin and the curing agent exhibit affinity and the mixture thereof exists in a uniform state. More specifically, for example, an epoxy resin and a curing agent are mixed at a weight ratio of 1/1, the mixture is completely dissolved at 120 ° C., and then the mixture obtained by stirring is allowed to stand for 30 minutes. Then, when a part of the mixed liquid is taken out and visually observed, it can be determined that the two are compatible when it can be confirmed that the mixture is a transparent liquid without phase separation. A liquid that is opaque due to phase separation is called "insoluble". Even if the combination has compatibility, if it takes a long time to dissolve, a large amount of heat energy is required for heating over a long period of time, which is disadvantageous in terms of productivity and cost.

  In the preliminary mixing step, it is preferable that white turbidity due to precipitates such as gel that is a reaction product of the epoxy resin and the curing agent does not occur. When precipitates are generated, the increase in viscosity is hindered. “No white turbidity caused by precipitates” means that there is no scattering of electromagnetic waves in the visible light region. More specifically, when fine particles having scattering centers that cause Rayleigh scattering, Mie scattering, and diffraction scattering phenomenon of light are not present in the mixture, it can be regarded as “no white turbidity due to precipitates”. Confirmation of the cloudiness of the mixture is, for example, by weighing 100 parts by weight of an epoxy resin and 120 parts by weight of a curing agent into a container made of heat-resistant glass, and using a heater with a fluid medium such as silicone oil or water as a container. It can carry out by the method of heating in the temperature range of 180 degreeC. The heating method is not limited to this, and a known method such as thermocouple or electromagnetic wave irradiation can be used, and ultrasonic waves or the like may be irradiated to promote dissolution.

  Part or all of the epoxy resin and the curing agent used in the thermosetting resin composition can be premixed. For example, when producing a thermosetting resin composition containing 100 parts by weight of an epoxy resin and 120 parts by weight of a curing agent, 50 parts by weight of the epoxy resin and 120 parts by weight of the curing agent are weighed in a container made of heat resistant glass. Next, the container is premixed by heating in a temperature range of 35 ° C. to ˜180 ° C. using a heater using a fluid such as silicone oil or water as a medium. The obtained preliminary mixture, the remaining 50 parts by weight of the epoxy resin, and the necessary amounts of the curing catalyst and the white pigment may be mixed by roll kneading or the like to produce a thermosetting resin composition.

  FIG. 1 is a perspective view showing an embodiment of an optical semiconductor device, and FIG. 2 is a sectional view taken along line II-II in FIG. The optical semiconductor device 1 shown in FIGS. 1 and 2 includes an optical semiconductor element mounting substrate 10 having a recess 11 composed of a bottom surface S1 and an inner peripheral side surface S2, and light mounted on the bottom surface S1, which is an optical semiconductor element mounting region. It is mainly composed of a semiconductor element 20 and a sealing resin layer 30 that covers the optical semiconductor element 20 in the recess 11.

  The optical semiconductor element mounting substrate 10 includes a plate-shaped metal wiring 12, a Ni / Ag plating 13 and a reflector 15 provided on the metal wiring 12. The Ni / Ag plating 13 constitutes the bottom surface S1. The reflector 15 has an inner peripheral side surface S2 that forms an opening through which the bottom surface S1 (Ni / Ag plating 13) is exposed. The reflector 15 is a resin molded product formed by molding the thermosetting resin composition according to the above-described embodiment.

  The optical semiconductor element 20 is electrically connected to the metal wiring 12 and the Ni / Ag plating 13 via the bonding wire 21. The metal wiring 12 is divided into a portion in contact with the bottom of the optical semiconductor element 20 and a portion to which the bonding wire 21 is connected. An insulating layer 16 is interposed between these two portions. The insulating layer 16 may be formed of the thermosetting resin composition according to the above-described embodiment.

  The sealing resin layer 30 includes a transparent resin layer 31 and a phosphor 32 dispersed in the transparent resin layer 31. The sealing resin layer 30 can be formed using a known transparent sealing resin composition containing a phosphor.

  The optical semiconductor device 1 includes, for example, a step of forming a light-curing thermosetting resin composition according to the above-described embodiment by transfer molding to form a resin molded product as the reflector 15 on the metal wiring 12, and a metal wiring. Manufactured by a method including a step of forming Ni / Ag plating 13 on electroplating 12, a step of mounting optical semiconductor element 20 on a semiconductor mounting region (bottom surface S <b> 1), and a step of forming sealing resin layer 30. can do. After the transfer molding, the optical semiconductor element 20 can be mounted without post-curing the formed resin molded product.

  The metal wiring 12 can be formed by a known method such as punching from a metal foil and etching. The metal wiring 12 is placed in a mold having a predetermined shape, and a thermosetting resin composition is injected from a resin injection port of the mold, and this is preferably performed at a mold temperature of 170 to 200 ° C. and a molding pressure of 0.5 to 20 MPa. A resin molded product can be obtained as the reflector 15 by a method of removing the mold after thermosetting for 60 to 120 seconds.

  The substrate for mounting an optical semiconductor element and the optical semiconductor element according to the present invention are not limited to the above-described embodiments, and can be appropriately modified without departing from the gist thereof. For example, as shown in the sectional view of FIG. 3, the optical semiconductor element 20 may be electrically connected to the metal wiring 12 and the Ni / Ag plating 13 via the solder bumps 22. Further, as shown in FIG. 4, a lead 40 may be used instead of using the metal wiring. In the optical semiconductor device 1 according to the embodiment shown in FIG. 4, the optical semiconductor element (LED element) 20 is bonded to the semiconductor element mounting substrate 10 with a die bond material 42. The optical semiconductor element mounting substrate may have two or more recesses.

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

Preparation of polyvalent carboxylic acid condensate The monomers for the repeating units and both end monomers shown in Examples A1, A2 and A3 below were refluxed in acetic anhydride for 30 minutes under a nitrogen atmosphere. Thereafter, the liquid temperature was raised to 160 ° C., and acetic acid and water produced by the reaction in an open system were distilled off in an open system under a nitrogen stream. When the generation of volatile components was not observed, melt condensation was performed at a temperature of 130 ° C. for 7 hours while reducing the pressure in the reaction vessel to obtain a polyvalent carboxylic acid condensate.
(Example A1)
Repeating unit: Hydrogenated terephthalic acid (manufactured by Tokyo Chemical Industry); 125 g
Both ends: hydrogenated trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company, product name H-TMAn); 126 g
(Example A2)
Repeating unit: hydrogenated terephthalic acid; 218 g
Both ends: hydrogenated trimellitic anhydride; 86 g
(Example A3)
Repeating unit: 1,3,5-tris (3-carboxypropyl) isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name C3CIC acid); 170 g
Both ends: hydrogenated trimellitic anhydride; 260 g

Characteristic evaluation of polyvalent carboxylic acid condensate The number average molecular weight, viscosity and softening point of the polyvalent carboxylic acid condensates of Examples A1, A2 and A3 were evaluated. The evaluation results are shown in Table 1.

The number average molecular weight Mn was measured using a standard polystyrene calibration curve by gel permeation chromatography (GPC) under the following conditions.
Apparatus: Pump (L-6200 manufactured by Hitachi, Ltd.), column (TSKgel-G5000HXL and TSKgel-G2000HXL, both are trade names manufactured by Tosoh Corporation), detector (L-3300RI manufactured by Hitachi, Ltd.)
-Eluent: Tetrahydrofuran-Temperature 30 ° C, Flow rate 1.0 ml / min

  Viscosity measurements were made using Research Equipment (London) LTD. This was carried out using an ICI cone plate viscometer made by the manufacturer. The softening point was evaluated by a method of heating the polyvalent carboxylic acid condensate on a hot plate and visually confirming the change in properties.

(Examples B1 to B11, Comparative Examples B1 to B4)
Preparation of Thermosetting Resin Composition After preliminarily mixing the epoxy resin and the curing agent, each material was blended according to the blending table shown in Table 2. After the blend is sufficiently mixed with a mixer, it is melt-kneaded under a predetermined condition with a mixing roll, the blend after cooling is pulverized and then pulverized, and the thermosetting properties of Examples B1 to B11 and Comparative Examples B1 to B4 A resin composition for light reflection was obtained. The unit of the blending amount of each component in the table is parts by weight, and the blank indicates that there is no blending.

Evaluation of Thermosetting Resin Composition The resin compositions of Examples and Comparative Examples were evaluated by the following various characteristic tests. The results are shown in Table 2.

Light reflectivity test The thermosetting resin compositions of each Example and each Comparative Example were transfer molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. The light reflectance at a wavelength of 400 nm of the molded product was measured using an integrating sphere spectrophotometer V-750 type (manufactured by JASCO Corporation). The light reflection characteristics were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2. Since Comparative Example B4 was not transfer moldable, the optical characteristics were evaluated using the cull portion.
(Evaluation criteria for light reflectance)
A: Light reflectance of 80% or more at a light wavelength of 400 nm B: Light reflectance of 70% or more and less than 80% at a light wavelength of 400 nm C: Light reflectance of less than 70% at a light wavelength of 400 nm

Storage modulus The thermosetting resin composition of each example and each comparative example was transfer molded 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, and a size of 10 × 80 × 3 mm. A molded product having was obtained. The dynamic viscoelasticity of the obtained molded product was measured under conditions of a temperature rising rate of 5 ° C./min using ARES2KSTD manufactured by TA Instruments (formerly Rheometric). From the measurement results, the storage elastic modulus (GPa) at 40 ° C. and 260 ° C. was determined. Furthermore, the storage elastic modulus of the test piece obtained by after-curing the molded product obtained by transfer molding at 150 ° C. for 3 hours was also obtained.

Glass transition temperature and linear expansion coefficient The thermosetting resin compositions of the examples and comparative examples were transfer molded under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. A molded product having a size of × 3 mm was obtained. The thermal expansion curve of a test piece having a size of 19 mm × 3 mm × 3 mm cut out from the molded product was measured under the condition of a temperature rising rate of 5 ° C./min. As a measuring device, TMASS6000 manufactured by Seiko Instruments Inc. was used. The glass transition temperature (hereinafter abbreviated as “Tg”) was determined based on the inflection point of the obtained linear expansion curve. Moreover, the inclination of the linear expansion curve in each area | region of the temperature below Tg and the temperature above Tg was calculated | required as a linear expansion coefficient. The linear expansion coefficient in the temperature region below Tg is abbreviated as α1, and the linear expansion coefficient in the temperature region above Tg is abbreviated as α2. Furthermore, the glass transition temperature and the linear expansion coefficient of a test piece obtained by after-curing the molded product obtained by transfer molding at 150 ° C. for 3 hours were also obtained in the same manner.

＊１：トリグリシジルイソシアヌレート（エポキシ当量１００、日産化学社製、商品名Ｔ ＥＰＩＣ−Ｓ）
＊２：ヘキサヒドロ無水フタル酸（和光純薬社製）
＊３：テトラ−ｎ−ブチルホスホニウム−ｏ，ｏ−ジエチルホスホロジチエート（日本化学工業社製、商品名ＰＸ−４ＥＴ）
＊４：トリメトキシエポキシシラン（東レダウコーニング社製、商品名Ａ−１８７）
＊５：溶融シリカ（電気化学工業社製、商品名ＦＢ−３０１）
＊６：中空粒子（住友３Ｍ社製、商品名Ｓ６〇−ＨＳ）
＊７：アルミナ（アドマテックス社製、商品名ＡＯ−８０２）

* 1: Triglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd., trade name T EPIC-S)
* 2: Hexahydrophthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
* 3: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (product name PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.)
* 4: Trimethoxyepoxysilane (manufactured by Toray Dow Corning, trade name A-187)
* 5: Fused silica (trade name FB-301, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 6: Hollow particles (manufactured by Sumitomo 3M, trade name S600-HS)
* 7: Alumina (manufactured by Admatechs, trade name AO-802)

  As shown in Table 2, the cured product (molded product) obtained by thermosetting the thermosetting resin composition of each example at a mold temperature of 180 ° C. for 90 seconds was subjected to after-curing. Thus, physical properties (storage modulus, Tg, and linear expansion coefficient) substantially equivalent to the cured product obtained by further proceeding the curing reaction were exhibited. Specifically, the rate of change of each physical property value was within ± 5% before and after the after cure. The values of storage elastic modulus, glass transition point, and linear expansion coefficient reflect the degree of crosslinking caused by the chemical reaction between the polyfunctional epoxy resin and the curing agent contained in the resin composition. When these physical property values change greatly before and after the after cure, it is considered that the crosslinking reaction of the cured product before the after cure has not sufficiently progressed.

  From the above experimental results, it can be seen that when the thermosetting resin composition of the present invention is cured, a post-curing step such as after-cure can be omitted. The thermosetting resin composition of the present invention has a moldability superior to that of conventional resin compositions, is extremely advantageous in terms of productivity, such as shortening the manufacturing time of a substrate for mounting an optical semiconductor, and is practically preferable.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device, 10 ... Substrate for optical semiconductor element mounting, 11 ... Recess, 12 ... Metal wiring, 15 ... Reflector, 16 ... Insulating layer, 20 ... Optical semiconductor element, 21 ... Bonding wire, 22 ... Solder bump, 30 DESCRIPTION OF SYMBOLS ... Sealing resin layer, 31 ... Transparent resin layer, 32 ... Phosphor, 40 ... Lead, 42 ... Die-bonding material, S1 ... Bottom surface (optical semiconductor element mounting area), S2 ... Inner peripheral side surface.

Claims (14)

An optical semiconductor element mounting substrate having a recess formed of a bottom surface and an inner peripheral side surface and having a resin molded product forming the inner peripheral side surface, wherein the bottom surface is an optical semiconductor element mounting region,
The resin molded product can be formed from a thermosetting resin composition containing an epoxy resin and a curing agent,
The degree of cure of a cured product obtained by transfer molding of the thermosetting resin composition at a mold temperature of 180 ° C. and a curing time of 90 seconds is further aftercured by heating at 150 ° C. for 3 hours. A substrate for mounting an optical semiconductor element, which is substantially equivalent to a cured product.   After the glass transition temperature of the cured product obtained by transfer molding the thermosetting resin composition under conditions of a mold temperature of 180 ° C. and a curing time of 90 seconds is further cured by heating at 150 ° C. for 3 hours. The substrate for mounting an optical semiconductor element according to claim 1, wherein the substrate is in a range of -5% to + 5% with respect to the cured product.   The storage elastic modulus at 40 ° C. of the cured product obtained by transfer molding of the thermosetting resin composition at a mold temperature of 180 ° C. and a curing time of 90 seconds is further cured by heating at 150 ° C. for 3 hours. The substrate for mounting an optical semiconductor element according to claim 1, wherein the substrate is in a range of −5% to + 5% with respect to the cured product.   The linear expansion coefficient in the glass region of the cured product obtained by transfer molding of the thermosetting resin composition at a mold temperature of 180 ° C. and a curing time of 90 seconds is further aftercured by heating at 150 ° C. for 3 hours. The optical-semiconductor element mounting substrate as described in any one of Claims 1-3 which exists in the range of -5%-+ 5% with respect to the said hardened | cured material after a long time. The optical semiconductor element mounting substrate according to claim 1, wherein the curing agent includes a polyvalent carboxylic acid condensate represented by the following general formula (1).

[In the formula (1), Rx represents a divalent group which has an aliphatic hydrocarbon ring and the aliphatic hydrocarbon ring may be substituted with a halogen atom or a linear or branched hydrocarbon group. A plurality of Rx in the same molecule may be the same or different, and Ry represents a monovalent hydrocarbon group which may be substituted with an acid anhydride group or a carboxylic acid ester group, and two Rx in the same molecule; Ry may be the same or different, and n1 represents an integer of 1 or more. ] Ry is selected from a monovalent group represented by the following chemical formula (20), or cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene, and hydrogenated biphenyl. The substrate for mounting an optical semiconductor element according to claim 5, which is a monovalent group derived by removing a hydrogen atom from a cyclic aliphatic hydrocarbon.

The substrate for mounting an optical semiconductor element according to claim 5 or 6, wherein the polyvalent carboxylic acid condensate represented by the general formula (1) is a compound represented by the following general formula (1a).

[In Formula (1a), m represents an integer of 0 to 4, Rz represents a halogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and when m is 2 to 4, Rz may be the same or different, and may be linked to each other to form a ring, and n1 represents an integer of 1 or more. ] Polyhydric carboxylic acid that can be obtained by a method in which the curing agent condenses a tricarboxylic acid compound represented by the following general formula (21) and a monocarboxylic acid compound represented by the following general formula (22) between molecules. The optical semiconductor element mounting substrate according to claim 1, comprising a condensate.

[In the formulas (21) and (22), R ₁ represents a trivalent group having an aliphatic hydrocarbon ring, a non-aromatic heterocyclic ring or a siloxane ring, and R ² represents an acid anhydride group or a carboxylic acid ester group. The monovalent hydrocarbon group which may be substituted is shown, and two R ² in the same molecule may be the same or different. ] The said tricarboxylic acid compound is an isocyanuric acid derivative represented by the following general formula (21a), and the said monocarboxylic acid compound is a hydrogenated trimellitic acid anhydride represented by the following chemical formula (22a). Substrate for mounting optical semiconductor elements.

[In the formula (21a), R ³ represents a saturated hydrocarbon group or an unsaturated hydrocarbon group. ] The optical semiconductor element mounting substrate according to any one of claims 5 to 9, wherein the curing agent further contains a polyvalent carboxylic acid condensate represented by the following chemical formula (3).

  The optical semiconductor element mounting substrate according to any one of claims 1 to 10, wherein the thermosetting resin composition further contains a curing catalyst.   The substrate for mounting an optical semiconductor element according to claim 11, wherein the content of the curing catalyst is in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and the curing agent. A method for manufacturing a substrate for mounting an optical semiconductor element according to any one of claims 1 to 12,
A production method comprising a step of forming the resin molded product by transfer molding the thermosetting resin composition. The substrate for mounting an optical semiconductor element according to any one of claims 1 to 12,
An optical semiconductor element mounted on the optical semiconductor element mounting region of the optical semiconductor element mounting substrate;
A sealing resin layer that covers the optical semiconductor element within the recess of the optical semiconductor element mounting substrate;
An optical semiconductor device comprising:

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