JP2014156591A - Thermosetting resin composition and cured product of the same, substrate for mounting optical semiconductor elements, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having an excellent releasability from a mold, endowed, when used as a reflector, with a high reflectivity, excellent in terms of heat resistance and light resistance, and capable of forming a tough cured product.SOLUTION: The provided thermosetting resin composition includes an epoxy resin (A), a curative (B), a white pigment (C), and whiskers (D), whereas the epoxy resin (A) is an epoxy resin expressed by the formula (1): [Rexpresses a p-valent organic group, whereas Rexpresses any of groups expressed by the formula (1a), unsaturated groups, hydroxyl group, and alkyloxy group-substituted ethyl groups, although at least one member of Ris a group expressed by the formula (1a), whereas p is an integer of 1 to 20, whereas q is an integer of 1 to 50, whereas the sum of q is 3 to 100].

Description

  The present invention relates to a thermosetting resin composition and a cured product thereof, an optical semiconductor element mounting substrate having a reflector formed of the cured product, and an optical semiconductor device having the substrate and the optical semiconductor element.

  2. Description of the Related Art In recent years, in various indoor or outdoor display boards, image reading light sources, traffic signals, large display units, etc., light emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources have been increasingly adopted. . As such an optical semiconductor device, in general, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (substrate for mounting an optical semiconductor element) and the optical semiconductor element is sealed with a transparent sealing material is widespread. doing. On the substrate in such an optical semiconductor device, a member (reflector) for reflecting light is formed in order to improve the extraction efficiency of light emitted from the optical semiconductor element.

  The reflector is required to have high light reflectivity. Conventionally, as a constituent material of the reflector, a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as an essential constituent unit is known (Patent Literature). 1-3).

  In addition, as the constituent material of the reflector, for example, thermosetting for light reflection containing, for example, a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0 in a specific ratio. Resin compositions are known (see Patent Document 4). Furthermore, it contains a thermosetting resin component and one or more filler components, and the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the volume ratio of each filler component A light-reflective thermosetting resin composition in which the calculated parameters are controlled within a specific range is known (see Patent Document 5).

JP 2000-204244 A JP 2004-75994 A JP 2006-257314 A JP 2010-235753 A JP 2010-235756 A

  The reflector is generally produced by subjecting a material (resin composition or the like) for forming the reflector to a molding method (molding method) using a mold such as transfer molding or compression molding. However, the reflector manufactured from the materials described in Patent Documents 1 to 5 described above is yellowed over time due to light or heat emitted from the semiconductor element in a light-emitting device using a high-power blue light semiconductor or white light semiconductor as a light source. However, the light reflectivity deteriorates over time. In addition, when continuous molding is performed in transfer molding, the mold releasability gradually decreases, and finally the mold releasability from the mold after molding such as application of the package or peeling from the lead frame occurs. Had the problem of being insufficient. For this reason, as a material for forming the reflector, there is currently a demand for a material that has a small decrease in light reflectivity due to heat and light and is excellent in releasability from a mold.

  In addition, the reflector is less likely to crack (crack) with respect to heat, light, and various stresses (for example, stress applied due to cutting or temperature change) generated from the optical semiconductor element. It is required to be tough, such as “may be referred to as“ crack resistance ”). This is because if the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it becomes difficult to ensure the reliability of the optical semiconductor device.

Accordingly, an object of the present invention is a thermosetting resin that is excellent in releasability from a mold, has high reflectivity (light reflectivity), is excellent in heat resistance and light resistance, and can form a tough cured product. It is to provide a composition.
Another object of the present invention is to provide a hardened product having excellent releasability from a mold, high reflectivity, excellent heat resistance and light resistance, and toughness.
Furthermore, another object of the present invention is to mount an optical semiconductor element having high productivity due to excellent releasability from the mold, excellent heat resistance and light resistance, high reflectivity, and having a tough reflector. It is to provide a substrate.
Another object of the present invention is to provide an optical semiconductor device having high light extraction efficiency and high durability.

  The above-described reflector is also required to have a linear expansion coefficient as low as possible in order not to cause problems such as peeling from the metal lead frame and warping of the lead frame as desirable characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have found that a thermosetting resin composition containing a specific epoxy resin, a curing agent, a white pigment, and a whisker is released from the mold. Resin composition for forming an optical semiconductor element mounting substrate and a reflector in an optical semiconductor device having the substrate, particularly capable of forming a toughened cured product with excellent reflectivity, high reflectance, excellent heat resistance and light resistance It was found useful as a product (a resin composition for forming a reflector), and the present invention was completed.

［式（１）中、Ｒ¹はｐ価の有機基を示す。ｐは、１〜２０の整数を示す。ｑは、１〜５０の整数を示し、式（１）におけるｑの和（総和）は、３〜１００の整数である。Ｒ²は、下記式（１ａ）〜（１ｃ）で表される基のいずれかを示す。但し、式（１）におけるＲ²の少なくとも１つは式（１ａ）で表される基である。

［式（１ｃ）中、Ｒ³は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルキルカルボニル基、又は置換若しくは無置換のアリールカルボニル基を示す。］］
で表されるエポキシ樹脂であることを特徴とする熱硬化性樹脂組成物を提供する。 That is, this invention contains an epoxy resin (A), a hardening | curing agent (B), a white pigment (C), and a whisker (D), and an epoxy resin (A) is a following formula (1).

[In the formula (1), R ¹ represents a p-valent organic group. p shows the integer of 1-20. q shows the integer of 1-50, and the sum (total) of q in Formula (1) is an integer of 3-100. R ² represents any one of groups represented by the following formulas (1a) to (1c). However, at least one of R ^{2 in} the formula (1) is a group represented by the formula (1a).

[In Formula (1c), R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. ]]
A thermosetting resin composition characterized by being an epoxy resin represented by the formula:

  Further, the epoxy resin (A) is prepared by using 1,2-epoxy-4- (2-oxiranyl) cyclohexane as an initiator with an organic compound having p hydroxyl groups in the molecule in the presence of a cationic catalyst containing a fluorine atom. The thermosetting resin composition is an epoxy resin produced by ring-opening polymerization and then epoxidizing with an oxidizing agent.

  Furthermore, the said thermosetting resin composition in which an epoxy resin (A) contains 100-30000 ppm of fluorine atoms is provided.

  Furthermore, the thermosetting resin composition, wherein the curing agent (B) is a liquid acid anhydride at 25 ° C., is provided.

  Furthermore, the thermosetting resin composition is provided, wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide and silica.

  Furthermore, the said thermosetting resin composition whose whisker (D) is at least 1 sort (s) selected from the group which consists of a zinc oxide whisker and a titanium oxide whisker is provided.

  Furthermore, the said thermosetting resin composition containing a fluorine-type mold release agent is provided.

  Furthermore, the said thermosetting resin composition in which the said fluorine-type mold release agent is an epoxy group containing fluorine substituted hydrocarbon is provided.

  Furthermore, the said thermosetting resin composition which is a resin composition for transfer molding or compression molding is provided.

  Furthermore, the said thermosetting resin composition which is a resin composition for reflector formation is provided.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said thermosetting resin composition.

  Moreover, this invention provides the board | substrate for optical semiconductor element mounting which has a reflector formed with the hardened | cured material of the said thermosetting resin composition.

  The present invention also provides an optical semiconductor device comprising the optical semiconductor element mounting substrate and an optical semiconductor element mounted on the substrate.

  Since the thermosetting resin composition of the present invention has the above-described configuration, by thermosetting the resin composition, it has excellent releasability from the mold, high reflectance, excellent heat resistance and light resistance, In addition, a tough cured product can be formed. Therefore, by using the thermosetting resin composition of the present invention as a resin composition for forming a reflector, it has high productivity because of its excellent releasability from the mold, has high reflectance, heat resistance and An optical semiconductor element mounting substrate having excellent light resistance and having a tough reflector can be obtained. Furthermore, by using the optical semiconductor element mounting substrate as a substrate of an optical semiconductor device, an optical semiconductor device with high light extraction efficiency and high durability can be obtained.

It is the schematic which shows an example of the board | substrate for optical semiconductor element mounting of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. It is the schematic (sectional drawing) which shows an example of the optical semiconductor device of this invention.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention contains an epoxy resin (A), a curing agent (B), a white pigment (C), and a whisker (D) as essential components, and the epoxy resin (A) contains The thermosetting resin composition is an epoxy resin represented by the following formula (1). The thermosetting resin composition of the present invention may contain other components as necessary in addition to the essential components.

[Epoxy resin (A)]
The epoxy resin (A) in the thermosetting resin composition of the present invention is an epoxy resin represented by the formula (1). In formula (1), R ¹ represents a p-valent organic group. p shows the integer of 1-20. Examples of the p-valent organic group include a p-valent organic group formed by removing p hydroxyl groups from an organic compound having p hydroxyl groups described later.

  In formula (1), q shows the integer of 1-50. In addition, when p is an integer greater than or equal to 2, several q may be the same and may differ. The sum (total) of q in Formula (1) is an integer of 3 to 100.

In formula (1), R ² is a substituent on the cyclohexane ring shown in the formula represents any of the groups represented by the following formula (1a) ~ (1c). The bonding position of R ² on the cyclohexane ring is not particularly limited. Usually, when the positions of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom are the 1st and 2nd positions, the 4th or 5th carbon atom It is. Further, if the epoxy resin represented by the formula (1) has a plurality of cyclohexane ring, the bonding position of R ² in each of the cyclohexane ring may be the same or different. At least one of R ^{2 in} the formula (1) is a group (epoxy group) represented by the formula (1a). That is, the epoxy resin (A) has at least one epoxy group in the molecule. In the case where the epoxy resin (A) has two or more R ^2, to a plurality of R ² may be the same or different.

In formula (1c), R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl. Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms such as a group. Examples of the alkylcarbonyl group include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl. Examples thereof include alkylcarbonyl groups such as a carbonyl group. Examples of the arylcarbonyl group include a benzoyl group and a naphthoyl group.

Examples of the substituent that the above-described alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms). Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C _1-6 alkoxy group, more preferably C _1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C _2-6 alkenyloxy group, more preferably C _2-4 alkenyloxy group) The aromatic ring may have a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group, such as a phenoxy group, a tolyloxy group, or a naphthyloxy group; Aryloxy groups (preferably C _6-14 aryloxy groups); aralkyloxy groups such as benzyloxy groups and phenethyloxy groups (preferably C _7-18 aralkyloxy group); acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group, benzoyloxy group (preferably C _1-12 acyloxy group); mercapto group; methylthio group, ethylthio group, etc. An alkylthio group (preferably a C _1-6 alkylthio group, more preferably a C _1-4 alkylthio group); an alkenylthio group such as an allylthio group (preferably a C _2-6 alkenylthio group, more preferably a C _2-4 alkenyl group). Thio group); phenylthio group, tolylthio group, naphthylthio group and the like, and aromatic rings have substituents such as C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. Arylthio groups (preferably C _6-14 arylthio groups); aralkylthio groups such as benzylthio groups and phenethylthio groups (preferably C _7-18 aralkylthio group); carboxy group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group (preferably C _1-6 alkoxy-carbonyl group); phenoxycarbonyl group, tolyloxy Aryloxycarbonyl groups such as carbonyl group and naphthyloxycarbonyl group (preferably C _6-14 aryloxy-carbonyl group); aralkyloxycarbonyl groups such as benzyloxycarbonyl group (preferably C _7-18 aralkyloxy-carbonyl group) Amino group; mono- or dialkylamino group (preferably mono- or di-C _1-6 alkylamino group) such as methylamino group, ethylamino group, dimethylamino group, diethylamino group; acetylamino group, propionylamino group, benzoyl A An acylamino group such as a mino group (preferably a C _1-11 acylamino group); an oxetanyl group-containing group such as an ethyloxetanyloxy group; an acyl group such as an acetyl group, a propionyl group or a benzoyl group; an oxo group; And a group bonded via a C _1-6 alkylene group.

The ratio of the group (epoxy group) represented by the formula (1a) to the total amount (100 mol%) of R ^{2 in} the epoxy resin represented by the formula (1) is not particularly limited, but is 40 mol% or more (for example, 40 to 100 mol%), preferably 60 mol% or more, and more preferably 80 mol% or more. When the ratio is less than 40 mol%, the heat resistance and mechanical properties of the cured product may be insufficient. The ratio can be calculated by, for example, ¹ H-NMR spectrum measurement or oxirane oxygen concentration measurement.

The epoxy resin (A) (epoxy resin represented by the formula (1)) is not particularly limited, but an organic compound [R ¹ (OH) _p ] having p hydroxyl groups in the molecule is used as an initiator (ie, Ring opening polymerization of 1,2-epoxy-4- (2-oxiranyl) cyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) starting from the hydroxyl group (active hydrogen) of the compound (Cation polymerization), and then epoxidized with an oxidizing agent. In particular, the epoxy resin (A) is an organic compound having p hydroxyl groups in the molecule in the presence of a cationic polymerization catalyst containing a fluorine atom from the viewpoint of releasability during molding. An epoxy resin produced by ring-opening polymerization of epoxy-4- (2-oxiranyl) cyclohexane and then epoxidizing with an oxidizing agent is preferable.

Examples of the organic compound [R ¹ (OH) _p ] having p hydroxyl groups in the molecule include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol; aromatics such as benzyl alcohol Group alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, Neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane (2,2-bis (hydroxymethyl) -1-butanol), penta Polyhydric alcohols such as lithritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S; phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4 ′ -Phenols such as dihydroxybenzophenone, bisphenol S, phenol novolac resin, cresol novolac resin; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, acrylic polyol resin, styrene-allyl alcohol copolymer resin, polyester polyol resin, polycaprolactone Polyol resin, polypropylene polyol, polytetramethylene glycol, polycarbonate polyols, hydroxyl group Polybutadiene, cellulose, cellulose acetate, cellulose acetate butyrate, oligomers or polymers having a hydroxyl group such as cellulosic polymers such as hydroxyethyl cellulose and the like.

  The 1,2-epoxy-4- (2-oxiranyl) cyclohexane can be produced by a known or conventional method, and is not particularly limited. For example, 4-vinylcyclohexene obtained by dimerization reaction of butadiene is converted to peracetic acid or the like. It is obtained by partial epoxidation using an oxidizing agent. Moreover, as 1,2-epoxy-4- (2-oxiranyl) cyclohexane, a commercial item can also be used.

  Examples of the cationic polymerization catalyst containing a fluorine atom include Bronsted acid and Lewis acid having a fluorine atom, and are not particularly limited. For example, boron trifluoride, boron trifluoride etherate (for example, boron trifluoride). Of diethyl ether complex). Although the usage-amount of the cationic polymerization catalyst containing a fluorine atom is not specifically limited, 0.01-10 weight part (preferably 0 with respect to 100 weight part of 1, 2- epoxy-4- (2-oxiranyl) cyclohexane). .1 to 5 parts by weight).

  The temperature (reaction temperature) for ring-opening polymerization of 1,2-epoxy-4- (2-oxiranyl) cyclohexane is not particularly limited, but is preferably -70 to 200 ° C, more preferably -30 to 100 ° C. is there. The reaction time can be appropriately adjusted according to the conversion rate of 1,2-epoxy-4- (2-oxiranyl) cyclohexane.

  The ring-opening polymerization of 1,2-epoxy-4- (2-oxiranyl) cyclohexane can also proceed in a solvent. As the solvent, those having active hydrogen cannot be used. That is, examples of the solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether; aliphatic hydrocarbons such as hexane and heptane; Ester etc. can be used. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

［式（２）中、Ｒ¹、ｐ、ｑは、前記に同じ。］ The compound represented by the following formula (2) (having a vinyl group) is obtained by ring-opening polymerization of 1,2-epoxy-4- (2-oxiranyl) cyclohexane using the organic compound having p hydroxyl groups as an initiator. Resin). The compound can be directly subjected to the next reaction (epoxidation) or can be purified and then subjected to the next reaction. The purification means is not particularly limited, and for example, a known or commonly used method such as a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these is used. it can.

[In the formula (2), R ¹ , p and q are the same as above. ]

  More specifically, the above ring-opening polymerization can be carried out according to the method described in, for example, JP-A-60-161973.

  Next, an epoxy resin (A) (an epoxy resin represented by the formula (1)) is obtained by epoxidizing the vinyl group of the compound represented by the formula (2) with an oxidizing agent.

  The oxidizing agent may be a known or commonly used oxidizing agent such as hydrogen peroxide or organic peracid, and is not particularly limited. Examples of the organic peracid include formic acid, peracetic acid, and perbenzoic acid. And trifluoroperacetic acid. Among them, peracetic acid is preferable because it is industrially available at low cost and has high stability. In addition, an oxidizing agent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  When the compound represented by the formula (2) is reacted (epoxidized) with an organic peracid, a known or commonly used catalyst may be used. Examples of the catalyst include alkalis such as sodium carbonate and acids such as sulfuric acid.

  The reaction (epoxidation) can be carried out by determining the presence or absence of solvent use or adjusting the reaction temperature according to the equipment used and the physical properties of the raw materials.

  The temperature (reaction temperature) for proceeding the above reaction can be appropriately determined depending on the reactivity of the oxidizing agent to be used, and is not particularly limited. For example, when peracetic acid is used as the oxidizing agent, 0 to 70 is used. It is preferable to set it as ° C. When the reaction temperature is less than 0 ° C., the progress of the reaction may be too slow. On the other hand, when the reaction temperature exceeds 70 ° C., decomposition of peracetic acid may easily occur.

  In the above reaction, a solvent can be used for the purpose of reducing the viscosity of the raw material or stabilizing by diluting the oxidizing agent. When peracetic acid is used as an oxidizing agent, for example, as a solvent, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether; esters such as ethyl acetate; acetone, methyl isobutyl ketone, and methyl ethyl ketone Etc. can be used.

  The amount of the oxidizing agent used (the charged molar ratio) relative to the vinyl group of the compound represented by formula (2) in the above reaction is not particularly limited. For example, when peracetic acid is used as the oxidizing agent, the vinyl group The amount of use is preferably 1 to 1.5 times mol.

  By the above reaction, a part or all of the vinyl group of the compound represented by the formula (2) is epoxidized and converted into a group (epoxy group) represented by the formula (1a). An epoxy resin (epoxy resin (A)) represented by In addition, the group represented by the formula (1c) in the formula (1) is, for example, an organic acid (for example, acetic acid) generated by a reaction between a vinyl group of the compound represented by the formula (2) and an organic peracid, Water, alcohol, etc. present in the system are generated by reacting with the group represented by the formula (1a) (side reaction). In addition, the ratio (ratio) of the groups represented by the formulas (1a) to (1c) in the formula (1) is, for example, the type of oxidizing agent, the amount of oxidizing agent used (molar ratio of oxidizing agent to vinyl group), It can be appropriately adjusted depending on the reaction conditions.

  The epoxy resin (A) obtained by the above reaction is, for example, a known or commonly used separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. It can be purified by the method.

  The epoxy resin (A) may be composed of one type of epoxy resin represented by the formula (1), or may be composed of two or more types of epoxy resins represented by the formula (1). It may be done.

  Although the weight average molecular weight of standard epoxy conversion of an epoxy resin (A) is not specifically limited, 300-100,000 are preferable, More preferably, it is 1000-10000. If the weight average molecular weight is less than 300, the mechanical strength and heat resistance of the cured product may be insufficient. On the other hand, if the weight average molecular weight exceeds 100,000, the viscosity may increase and the fluidity during molding may decrease. The weight average molecular weight can be measured by, for example, a gel permeation chromatography (GPC) method.

  Although the epoxy equivalent of an epoxy resin (A) is not specifically limited, 50-1000 are preferable, More preferably, it is 100-500. If the epoxy equivalent is less than 50, the cured product may become brittle. On the other hand, if the epoxy equivalent exceeds 1000, the mechanical strength of the cured product may be insufficient. The epoxy equivalent can be measured according to, for example, JIS K7236: 2001.

The epoxy resin (A) is not particularly limited, but may contain a fluorine atom. For example, when the ring-opening polymerization proceeds in the presence of a cationic polymerization catalyst containing a fluorine atom, the resulting epoxy resin (A) tends to contain a fluorine atom. Although content of the fluorine atom in an epoxy resin (A) is not specifically limited, 100-30000 ppm is preferable, More preferably, it is 2000-15000 ppm. If the fluorine atom content is less than 100 ppm, the releasability of the cured product from the mold may be insufficient. On the other hand, if the fluorine atom content exceeds 30000 ppm, peeling from the lead frame or peeling from the sealing resin may easily occur. In addition, content of a fluorine atom can be measured by combustion ion chromatography etc., for example. In addition, the form in which the fluorine atom is contained in the epoxy resin (A) includes, for example, an aspect included as a constituent element of the epoxy resin, an aspect included as a constituent element of a component (such as an impurity) different from the epoxy resin, and the like. Although it is not specifically limited, For example, you may contain in the aspect substituted by at least 1 of the hydrogen atom couple | bonded with the carbon atom in the epoxy resin represented by Formula (1). The presence of the C—F bond in the epoxy resin represented by the formula (1) is confirmed by, for example, ¹ H-NMR spectrum measurement.

  As an epoxy resin (A), commercial items, such as a brand name "EHPE3150" (made by Daicel Corporation), can also be used, for example. Moreover, in the thermosetting resin composition of this invention, an epoxy resin (A) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Although content (blending amount) of the epoxy resin (A) in the thermosetting resin composition of the present invention is not particularly limited, it is 2 to 20 wt% with respect to the total amount (100 wt%) of the thermosetting resin composition. % Is preferable, more preferably 4 to 15% by weight, still more preferably 6 to 10% by weight. When the content of the epoxy resin (A) is less than 2% by weight, the fluidity of the compound (thermosetting resin composition) may be insufficient and may be unfilled by transfer molding. On the other hand, when the content of the epoxy resin (A) exceeds 20% by weight, the linear expansion coefficient of the cured product increases, and warpage may easily occur between the lead frame and the lead frame.

  The ratio of the epoxy resin (A) to the total amount (100 wt%) of the epoxy compound (epoxy resin) contained in the thermosetting resin composition of the present invention is not particularly limited, but is 50 wt% or more (for example, 50 to 100). % By weight) is preferred, more preferably 90% by weight or more. When the proportion of the epoxy resin (A) is less than 50% by weight, the releasability during continuous molding tends to decrease, and the heat resistance and light resistance (yellowing resistance) of the cured product tend to be insufficient.

[Other epoxy compounds]
The thermosetting resin composition of the present invention may contain an epoxy compound other than the epoxy resin (A) (sometimes referred to as “other epoxy compounds”) as long as the effects of the present invention are not impaired. Examples of the other epoxy compounds include known and commonly used epoxy compounds, and are not particularly limited. For example, aromatic glycidyl ether type epoxy compounds [for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, biphenol type epoxies. Compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A cresol novolac type epoxy compounds, naphthalene type epoxy compounds, epoxy compounds obtained from trisphenol methane, etc.]; aliphatic glycidyl ether type An aliphatic epoxy compound such as an epoxy compound [eg, aliphatic polyglycidyl ether]; (i) two adjacent carbon atoms constituting an alicyclic ring (aliphatic hydrocarbon ring) and an oxygen atom Examples thereof include compounds having an epoxy group (alicyclic epoxy group) composed of a kid, and (ii) alicyclic epoxy compounds such as hydrogenated aromatic glycidyl ether-based epoxy compounds. In addition, another epoxy compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The above-mentioned (i) compound having an alicyclic epoxy group can be arbitrarily selected from known or commonly used compounds. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable. That is, (i) the compound having an alicyclic epoxy group is preferably a compound having a cyclohexene oxide group from the viewpoint of transparency and heat resistance of the cured product, and particularly a compound represented by the following formula (I) (aliphatic Cyclic epoxy compounds) are preferred.

  In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.

  Examples of the compound in which X in the formula (I) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane and the like.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

  As the linking group X, a linking group containing an oxygen atom is particularly preferable. Specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-; A group in which a plurality of groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

Typical examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). In the following formulas (I-5) and (I-7), l and m each represent an integer of 1 to 30. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (I-9) and (I-10) each represent an integer of 1 to 30.

  (Ii) Examples of the hydrogenated glycidyl ether-based epoxy compound include 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane and 2,2-bis [3,5-dimethyl-4. A compound obtained by hydrogenating a bisphenol A type epoxy compound such as (2,3-epoxypropoxy) cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) Cyclohexyl] methane, bis [o, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3 A compound obtained by hydrogenating a bisphenol F-type epoxy compound such as 5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane ( Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; Examples thereof include hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane.

  The content (blending amount) of the other epoxy compound in the thermosetting resin composition of the present invention is not particularly limited, but the total amount (100 wt%) of the epoxy compound (epoxy resin) contained in the thermosetting resin composition. Is less than 50% by weight (for example, 0% by weight or more and less than 50% by weight), more preferably less than 10% by weight. When the content of the other epoxy compound is 50% by weight or more, there is a tendency that the releasability at the time of continuous molding is lowered or the heat resistance and light resistance (yellowing resistance) of the cured product are insufficient.

[Curing agent (B)]
The curing agent (B) in the thermosetting resin composition of the present invention is a compound having a function of reacting with a compound having an epoxy group such as an epoxy resin (A) to cure the thermosetting resin composition. As the curing agent (B), a known or conventional curing agent can be used as a curing agent for an epoxy resin, and is not particularly limited. For example, an acid anhydride curing agent, an amine curing agent, and an imidazole curing agent. And polymercaptan curing agents. In addition, a hardening | curing agent (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Especially, as a hardening | curing agent (B), an acid anhydride type hardening | curing agent is preferable.

  Examples of the acid anhydride-based curing agent include acid anhydrides that are liquid at 25 ° C. such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like. Examples thereof include solid acid anhydrides at 25 ° C. such as phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride. In addition, the said acid anhydride type hardening | curing agent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  A commercial item can also be used as a hardening | curing agent (B). For example, as a commercial product of the above acid anhydride curing agent, trade names “Licacid MH-700”, “Licacid MH-700F”, “Licacid HH” (hereinafter, Shin Nippon Rika Co., Ltd.); -5500 "(manufactured by Hitachi Chemical Co., Ltd.).

  The content (blending amount) of the curing agent (B) in the thermosetting resin composition of the present invention is not particularly limited, but is preferably 50 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Preferably it is 70-150 weight part. More specifically, the curing agent (B) is a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compounds having all epoxy groups contained in the thermosetting resin composition of the present invention. Is preferably used. When the content of the curing agent (B) is less than 50 parts by weight, the progress of curing becomes insufficient, and the toughness of the cured product may be insufficient, or the yellowing resistance of the cured product may be reduced. On the other hand, when the content of the curing agent (B) exceeds 200 parts by weight, the curing is similarly insufficient, and the cured product may be colored to easily deteriorate the hue.

[Curing accelerator]
The thermosetting resin composition of the present invention may further contain a curing accelerator. The said hardening accelerator is a compound which has a function which accelerates | stimulates a cure rate, when the compound which has epoxy groups, such as an epoxy resin (A), hardens | cures with a hardening | curing agent (B). As the curing accelerator, known or conventional curing accelerators can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, a phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate salt); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (for example, phenol salt, octylate) , P-toluenesulfonate, formate, tetraphenylborate salt); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; Imidazoles such as ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Phosphines such as Li triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p- tolyl) borate, organic metal salts such as zinc octylate and tin octylate; metal chelate and the like. In addition, a hardening accelerator can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Further, as the curing accelerator, for example, trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “12XD” (developed product) ( Product name “TPP-K”, “TPP-MK” (above, manufactured by Hokuko Chemical Co., Ltd.); Product name “PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) Commercial products such as these can also be used.

  The content (blending amount) of the curing accelerator in the thermosetting resin composition of the present invention is not particularly limited, but is preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Preferably it is 0.3-5 weight part. If the content of the curing accelerator is less than 0.1 parts by weight, curing may be insufficient in transfer molding. On the other hand, when the content of the curing accelerator exceeds 8 parts by weight, the storage stability may be deteriorated, or the cured product may be colored to easily deteriorate the hue.

[White pigment (C)]
The white pigment (C) in the thermosetting resin composition of the present invention particularly imparts high light reflectivity to a cured product obtained by curing the thermosetting resin composition, and controls the content. By doing, it plays the role which reduces the linear expansion coefficient of hardened | cured material. As the white pigment (C), known or commonly used white pigments can be used, and are not particularly limited. For example, glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acidic clay, active Inorganic white pigments such as clay, boehmite, pseudoboehmite, inorganic oxides, metal salts such as alkaline earth metal salts; styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amide resins, etc. White pigments such as resin pigments (plastic pigments); hollow particles having a hollow structure (balloon structure), and the like. In addition, a white pigment (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Examples of the inorganic oxide include aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide (rutile titanium oxide, anatase titanium oxide, brookite titanium oxide), zirconium oxide, zinc oxide, silicon oxide (silica). ) And the like. Examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and sulfuric acid. Barium etc. are mentioned. Examples of the metal salt other than the alkaline earth metal salt include aluminum silicate, aluminum hydroxide, and zinc sulfide.

  Although it does not specifically limit as said hollow particle, For example, metal oxides, such as inorganic glass (for example, sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.), silica, an alumina, calcium carbonate, barium carbonate, Inorganic hollow particles composed of inorganic materials such as nickel carbonate and calcium silicate (including natural products such as Shirasu Balloon); styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride -Based resins, vinylidene chloride-based resins, amide-based resins, urethane-based resins, phenol-based resins, styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefin-based polymers (including cross-linked products of these polymers), etc. Organic hollow particles composed of organic materials; hybrid materials of inorganic and organic materials Configured inorganic - organic hollow particles, and the like. In addition, the said hollow particle may be comprised from the single material, and may be comprised from 2 or more types of materials. In addition, the hollow portion of the hollow particles (the space inside the hollow particles) may be in a vacuum state or may be filled with a medium. However, particularly from the viewpoint of improving the reflectance, the refractive index is low. Hollow particles filled with a medium (for example, an inert gas such as nitrogen or argon or air) are preferred.

  The white pigment (C) is subjected to a known or conventional surface treatment (for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone). It may be what was done. By performing such a surface treatment, there are cases where compatibility and dispersibility with other components in the thermosetting resin composition can be improved.

  Among them, the white pigment (C) is preferably an inorganic oxide (for example, aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, silicon oxide, etc.) from the viewpoints of availability, heat resistance, and light resistance. More preferred are titanium oxide and silicon oxide (silica).

  The white pigment (C) can be produced by a known or conventional production method. Moreover, as a white pigment (C), a commercial item can also be used, for example, brand name "SR-1", "R-42", "R-45M", "R-650", "R-32". ”,“ R-5N ”,“ GTR-100 ”,“ R-62N ”,“ R-7E ”,“ R-44 ”,“ R-3L ”,“ R-11P ”,“ R-21 ”, "R-25", "TCR-52", "R-310", "D-918", "FTR-700" (manufactured by Sakai Chemical Industry Co., Ltd.), trade name "Taipeke CR-50", "CR-50-2", "CR-60", "CR-60-2", "CR-63", "CR-80", "CR-90", "CR-90-2", "CR -93 "," CR-95 "," CR-97 "(manufactured by Ishihara Sangyo Co., Ltd.), trade names" JR-301 "," JR-403 "," JR-405 " “JR-600A”, “JR-605”, “JR-600E”, “JR-603”, “JR-805”, “JR-806”, “JR-701”, “JRNC”, “JR-800” ", JR" (manufactured by Teika Co., Ltd.), trade names "TR-600", "TR-700", "TR-750", "TR-840", "TR-900" (above, Fuji Manufactured by Titanium Industry Co., Ltd.), trade names “KR-310”, “KR-380”, “KR-380N”, “ST-410WB”, “ST-455”, “ST-455WB”, “ST-457SA” ”,“ ST-457EC ”,“ ST-485SA15 ”,“ ST-486SA ”,“ ST-495M ”(above, manufactured by Titanium Industry Co., Ltd.), etc .; trade name“ A-110 ”, "TCA-123E", "A-19 ”,“ A-197 ”,“ SA-1 ”,“ SA-1L ”,“ SSP series ”,“ CSB series ”(manufactured by Sakai Chemical Industry Co., Ltd.), trade names“ JA-1 ”,“ "JA-C", "JA-3" (manufactured by Teika Co., Ltd.), trade names "KA-10", "KA-15", "KA-20", "STT-65C-S", "STT" -30EHJ "(above, manufactured by Titanium Industry Co., Ltd.), trade names" DCF-T-17007 "," DCF-T-17008 "," DCF-T-17050 "(above, manufactured by Resino Color Industry Co., Ltd.), etc. Anatase type titanium oxide; FB series (namely, manufactured by Denki Kagaku Kogyo Co., Ltd.) such as “FB910” and “FB940”, “MSR-2212”, “MSR25” (named, Tatsumori Co., Ltd.) , “HS-105”, “HS-106”, “HS-107” Silica such as (manufactured by Micron) can be used.

  The shape of the white pigment (C) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fibrous shape, a needle shape, and a scale shape. Among these, from the viewpoint of dispersibility of the white pigment (C), a spherical white pigment is preferable, and a true spherical white pigment (for example, a spherical white pigment having an aspect ratio of 1.2 or less) is particularly preferable.

  Although the center particle diameter of a white pigment (C) is not specifically limited, 0.1-50 micrometers is preferable from a viewpoint of the light reflectivity improvement of hardened | cured material. In particular, when an inorganic oxide is used as the white pigment (C), the center particle diameter of the inorganic oxide is not particularly limited, but is preferably 0.1 to 50 μm, and more preferably 0.1 to 30 μm. In addition, the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.

  The content (blending amount) of the white pigment (C) in the thermosetting resin composition of the present invention is not particularly limited, but is 65% by weight or more (for example, with respect to the thermosetting resin composition (100% by weight)). 65 to 90% by weight), more preferably 75% by weight or more (for example, 75 to 90% by weight). If the content of the white pigment (C) is less than 65% by weight, the linear expansion coefficient may increase and the lead frame may be easily warped. On the other hand, if the content of the white pigment (C) exceeds 90% by weight, the fluidity of the blend may be insufficient and become unfilled.

  When titanium oxide is used as the white pigment (C), the content (blending amount) of the titanium oxide is the total amount of the white pigment (C) in terms of the balance between yellowing resistance of the cured product and light reflectivity. 5 to 40% by weight is preferable with respect to (100% by weight), more preferably 10 to 35% by weight. When the content of titanium oxide is less than 5% by weight, the light reflectivity of the cured product may be insufficient. On the other hand, when the content of titanium oxide exceeds 40% by weight, the fluidity of the blend may be insufficient, or the cured product may be easily yellowed due to heating or aging. In particular, when titanium oxide is used as the white pigment (C), it is preferable to use silica together.

[Whisker (D)]
The whisker (D) in the thermosetting resin composition of the present invention particularly imparts toughness to a cured product obtained by curing the thermosetting resin composition, and releasability from the mold. Play a role to improve. In addition, there is an effect of suppressing the generation of burrs during molding. As the whisker (D), known or conventional whiskers can be used, and are not particularly limited. However, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, silicon carbide whisker, silicon nitride whisker, magnesium oxide whisker, Magnesium borate whisker, basic magnesium sulfate whisker, titanium diboride whisker, graphite whisker, calcium sulfate whisker, α-alumina whisker, chrysotile whisker, wollastonite whisker, calcium carbonate whisker, aluminum silicate whisker, calcium silicate whisker , Titanium oxide whiskers, zirconium oxide whiskers and the like. In addition, a whisker (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Especially, as a whisker (D), a zinc oxide whisker and a titanium oxide whisker are preferable from the viewpoint of toughness of a hardened | cured material and mold release property.

  The whisker (D) is subjected to a known or conventional surface treatment (for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone). It may be. By performing such a surface treatment, there are cases where compatibility and dispersibility with other components in the thermosetting resin composition can be improved.

  As the whisker (D), for example, trade names “Panatetra WZ-0501”, “Panatetra WZ-0501L”, “Panatetra WZ-0511”, “Panatetra WZ-0511L”, “Panatetra WZ-0531”, “Panatetra” "WZ-05E1", "Panatetra WZ-05F1" (Zinc oxide whisker, manufactured by Amtec Co., Ltd.); trade names "FTL-100", "FTL-110", "FTL-200", "FTL-300" Commercial products such as titanium oxide whisker (manufactured by Ishihara Sangyo Co., Ltd.) can also be used.

  Although the needle-like fiber length of a whisker (D) is not specifically limited, 0.1-100 micrometers is preferable, More preferably, it is 1-80 micrometers. Although the needle-like fiber diameter (diameter) of a whisker (D) is not specifically limited, 0.05-10 micrometers is preferable, More preferably, it is 0.1-5 micrometers. In addition, the needle-like fiber length and the needle-like fiber diameter of the whisker (D) can be measured by observation with an electron microscope (for example, TEM or the like) dispersed in a solvent such as alcohol. Moreover, it can measure also by burning a thermosetting resin composition or its hardened | cured material, and observing a residue with an electron microscope (for example, SEM etc.).

  The whisker (D) content (blending amount) in the thermosetting resin composition of the present invention is not particularly limited, but is 0.5 to 8% by weight with respect to the thermosetting resin composition (100% by weight). Is preferable, and more preferably 1 to 4% by weight. When the whisker (D) content is less than 0.5% by weight, the effect of suppressing burrs during molding becomes poor, and the toughness and releasability of the cured product may be insufficient. On the other hand, if the content of the whisker (D) exceeds 8% by weight, the fluidity of the blend may be lowered and become unfilled.

[Antioxidant]
The thermosetting resin composition of the present invention may further contain an antioxidant. As the antioxidant, known or commonly used antioxidants can be used, and are not particularly limited. For example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), Examples thereof include phosphorus antioxidants (phosphorus compounds) and sulfur antioxidants (sulfur compounds).

  Examples of the phenol-based antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- ( Monophenols such as 3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [ 1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxas B Bisphenols such as [5.5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl- 4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, polymer type phenols such as tocophenol, and the like.

  Examples of the hindered amine antioxidant include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl]. Methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t -Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis ( 2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Phosphites; 9,10 Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene Examples include oxaphosphaphenanthrene oxides such as -10-oxide.

  Examples of the sulfur-based antioxidant include dodecanethiol, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl-3,3′-thiodipropionate. Etc.

  In addition, an antioxidant can also be used individually by 1 type and can also be used in combination of 2 or more type. Examples of the antioxidant include, for example, trade name “Irganox 1010” (manufactured by BASF, phenolic antioxidant), trade name “AO-60” (manufactured by ADEKA, phenolic antioxidant), trade name “ Commercial products such as “Irgafos 168” (manufactured by BASF, phosphorous antioxidant) and trade name “Adeka Stub HP-10” (manufactured by ADEKA, Inc., phosphorous antioxidant) can also be used.

  Among them, as the antioxidant, a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant are preferable. In particular, a phenolic antioxidant and a phosphorus antioxidant or a sulfur antioxidant are used in combination. It is preferable to do.

  The content (blending amount) of the antioxidant in the thermosetting resin composition of the present invention is not particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Preferably it is 0.5-3 weight part. When the content of the antioxidant is less than 0.1 parts by weight, the effect of adding is poor and yellowing resistance may not be improved. On the other hand, when content of antioxidant exceeds 5 weight part, hardened | cured material may color and a hue may deteriorate.

[Fluorine release agent]
The thermosetting resin composition of the present invention may further contain a fluorine-based mold release agent. As the above-mentioned fluorine-based mold release agent, a known or conventional fluorine-type mold release agent can be used, and is not particularly limited. For example, a fluorine atom and a reactive group (for example, epoxy group, (meth)) in the molecule. An acryloyl group, an amino group, an alkoxysilyl group, etc.). More specifically, as the fluorine-based mold release agent, for example, an epoxy compound having a fluoroalkyl group (an alkyl group in which some or all of hydrogen atoms are substituted with fluorine atoms); a fluoroalkyl group (meth) Examples include acrylates; amines having a fluoroalkyl group; hydrolyzable group-containing silicates having a fluoroalkyl group. Among these, an epoxy compound having a fluoroalkyl group and a hydrolyzable silicate having a fluoroalkyl group are preferable.

Examples of the epoxy compound having a fluoroalkyl group include a fluorine-substituted hydrocarbon having an epoxy group (epoxy group-containing fluorine-substituted hydrocarbon), and more specifically, for example, represented by the following formula (3). (Monofunctional epoxy compound having fluoroalkyl) and the like.

R in the above formula (3) represents an integer of 1 to 15. Moreover, s shows the integer of 1-5. Y represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group. Examples of the fluoroalkyl group include alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10) in which part or all of hydrogen atoms are substituted with fluorine atoms [for example, trifluoromethyl group and perfluoroisopropyl group. Etc.]. In addition, — (CH ₂ ) _r — in the formula (3) may be one in which a part of the hydrogen atoms is substituted with a hydroxyl group, or may contain an ether bond in the middle. Good. More specifically, the compound represented by the formula (3) is a compound represented by the following formula (2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7-tridecafluoroheptyloxirane) and the like.

  Examples of the epoxy compound having a fluoroalkyl group include trade names “E-1430”, “E-1630”, “E-1830”, “E-2030”, “E-3430”, and “E-3630”. , "E-3830", "E-4030", "E-5244", "E-5444", "E-5644", "E-5844" (above, manufactured by Daikin Industries, Ltd.) (A commercially available product containing an epoxy compound having a fluoroalkyl group) can also be used.

Examples of the hydrolyzable group-containing silicate having a fluoroalkyl group include a compound represented by the following formula (4) (tetrafunctional fluorine-containing organosilicate) or a condensate thereof (oligomer); represented by the following formula (5). Compounds (bi- or trifunctional fluorine-containing organosilicates) or condensates thereof (oligomers); and further, co-condensates (co-oligomers) of tetrafunctional fluorine-containing organosilicates with 2-3 functional fluorine-containing organosilicates, etc. It is done.

R ⁴ in the above formula (4) may be the same or different and may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom, and may contain 1 to 20 carbon atoms (preferably 1 To 10) fluorine-containing hydrocarbon groups. Examples of the fluorinated hydrocarbon group include alkyl groups having 1 to 10 carbon atoms [for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group. Group, linear or branched alkyl group such as n-pentyl group, i-pentyl group, neopentyl group, n-hexyl group, i-hexyl group and n-octyl], aryl group having 1 to 10 carbon atoms [ For example, a group in which a part or all of hydrogen atoms in a hydrocarbon group such as a phenyl group, a toluyl group, a xylyl group, a substituted or unsubstituted aryl group such as a naphthyl group] is substituted with a fluorine atom can be mentioned. t shows the integer of 1-4. R < ⁵ > is the same or different and shows a C1-C10 hydrocarbon group. Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms [for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a linear or branched alkyl group such as an n-pentyl group, i-pentyl group, neopentyl group, n-hexyl group, i-hexyl group, n-octyl], an aryl group having 1 to 10 carbon atoms [for example, Substituted or unsubstituted aryl groups such as phenyl group, toluyl group, xylyl group, naphthyl group] and the like.

R < ⁶ > in the said Formula (5) is the same or different, shows a C1-C10 hydrocarbon group, for example, the thing similar to R < ⁵ > is illustrated. u represents 1 or 2. R ⁷ may be the same or different and may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom, and may contain 1 to 20 carbon atoms (preferably 1 to 10). A hydrocarbon group is exemplified, and examples thereof are the same as those for R ⁴ . v represents an integer of 1 to 3. The sum of u and v (u + v) is an integer of 2 to 4.

More specifically, R ^{4 to} R ⁷ in formulas (4) and (5) are linear or branched alkyl groups described in pages 7 to 8 of WO 97/11130, Examples thereof include a fluoroalkyl group, a fluorocarbonyl group, a fluoroether group, etc. Among them, — (CH ₂ ) _w H (wherein w is an integer of 0 to 6), —CH (CH ₃ ) ₂ , —CH ₂ (CF ₂ ) ₂ H, —CH ₂ (CF ₂ ) ₃ H, —CH ₂ (CF ₂ ) ₄ H, —CHFCF ₂ CF ₂ H, —CH ₂ CF ₃ , —CH ₂ CF ₂ CF ₃ , — _{CH 2 CF 2 CHFCF 3, -CH} 2 (CF 2) 2 CF 3, -CH 2 CH 2 (CF 2) 3 CF 3, -CH 2 CH 2 (CF 2) 7 CF 3, -C (= O) _{CF 3, -C (= O)} CF 2 CF 3, -C (= O) (CF 2) 6 CF 3, -C (= O) (CF 2) 7 C ₃ and the like are particularly preferred.

  As the hydrolyzable group-containing silicate having a fluoroalkyl group, for example, a commercial product such as trade name “Zeffle GH701” (manufactured by Daikin Industries, Ltd.) can be used. Examples of the hydrolyzable group-containing silicate having a fluoroalkyl group include one or two fluorine-containing organosilicates described in, for example, International Publication No. 96/26254, International Publication No. 97/11130, and the like. One or more of these (co) condensates can also be used.

  In addition, a fluorine-type mold release agent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The content (blending amount) of the fluorine-based mold release agent in the thermosetting resin composition of the present invention is not particularly limited, but is preferably 1 to 12 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Preferably it is 3-10 weight part. If the content of the fluorine-based mold release agent is less than 1 part by weight, the release property of the cured product may be insufficient. On the other hand, when the content of the fluorine-based release agent exceeds 12 parts by weight, the adhesion of the cured product to the lead frame may be reduced.

  The content (blending amount) of the fluorine-based mold release agent with respect to 100 parts by weight of the total amount of the epoxy group-containing compound (total amount of epoxy resin (A) and other epoxy compounds) contained in the thermosetting resin composition of the present invention is Although not particularly limited, 1 to 12 parts by weight is preferable, and 3 to 10 parts by weight is more preferable. If the content of the fluorine-based mold release agent is less than 1 part by weight, the release property of the cured product may be insufficient. On the other hand, when the content of the fluorine-based release agent exceeds 12 parts by weight, the adhesion of the cured product to the lead frame may be reduced.

[Additive]
The thermosetting resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired, in addition to the components described above. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly. In addition, as long as the viscosity and transparency are not impaired, an antifoaming agent, a leveling agent, a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, a surfactant, Conventional additives such as flame retardants, colorants, ion adsorbents, pigments, and phosphors (for example, inorganic phosphor particles such as YAG-based phosphor particles and silicate-based phosphor particles) can be used.

  Although the thermosetting resin composition of this invention is not specifically limited, It can prepare by mix | blending and knead | mixing each above-mentioned component in the heated state as needed. The kneading method is not particularly limited, and for example, known or conventional kneading means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used.

  When the thermosetting resin composition of the present invention is obtained as a solid at room temperature (for example, 25 ° C.), the thermosetting resin composition is particularly preferable as a resin composition for transfer molding or a resin composition for compression molding. Can be used. Specifically, for example, when preparing the thermosetting resin composition of the present invention, it can be used as a resin composition for transfer molding or compression molding by molding into a tablet shape.

  The thermosetting resin composition of the present invention is further heated to cause a part of the epoxy group-containing compound in the thermosetting resin composition to react to form a B-staged thermosetting resin composition ( A B-stage thermosetting resin composition) can also be obtained.

<Hardened product>
By curing the thermosetting resin composition of the present invention (or the thermosetting resin composition in a B-stage state) by heating, from a mold (for example, a transfer molding mold, a compression molding mold, etc.) An excellent releasability, high reflectivity, excellent heat resistance and light resistance, and a tough cured product (sometimes referred to as “cured product of the present invention”) can be obtained. Although the heating temperature (curing temperature) in the case of hardening is not specifically limited, 100-200 degreeC is preferable, More preferably, it is 150-190 degreeC. Moreover, the time (heating time) heated in the case of hardening is although it does not specifically limit, 40 to 300 seconds are preferable, More preferably, it is 60 to 120 seconds. When the curing temperature and curing time are lower than the lower limit of the above range, the curing is insufficient. Conversely, when the curing temperature and the curing time are higher than the upper limit of the above range, yellowing due to thermal decomposition occurs or the tact time becomes longer and the productivity Since it falls, neither is preferable. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Further, the heat curing treatment may be performed in one step (for example, transfer molding only), or may be further heated in an oven or the like as post-cure (secondary curing) after transfer molding.

<Resin-forming resin composition>
The thermosetting resin composition of the present invention is a material for forming a reflector (light reflecting member) of an optical semiconductor element substrate (an optical semiconductor element mounting substrate) in an optical semiconductor device (a resin composition for reflector formation). Can be preferably used. By using the thermosetting resin composition of the present invention as a resin composition for a reflector, it is excellent in releasability from the mold, so it has high productivity, high reflectivity, heat resistance and light resistance. An optical semiconductor element mounting substrate having an excellent and strong reflector can be manufactured.

<Optical semiconductor device mounting substrate>
The substrate for mounting an optical semiconductor element of the present invention comprises at least a reflector formed of a cured product of the thermosetting resin composition of the present invention (cured product obtained by curing the thermosetting resin composition of the present invention). It is a substrate which has. FIG. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, where (a) is a perspective view and (b) is a cross-sectional view. In FIG. 1, 100 is a reflector, 101 is a metal wiring (lead frame), and 102 is a mounting region of an optical semiconductor element. In the optical semiconductor element mounting substrate of the present invention, the reflector 100 has a concave shape that surrounds the optical semiconductor element mounting region 102 in an annular shape and is inclined so that the diameter of the ring increases upward. Yes. The substrate for mounting an optical semiconductor element of the present invention is only required to have at least the inner surface of the concave shape formed of a cured product of the thermosetting resin composition of the present invention.

  A method for forming the reflector in the substrate for mounting an optical semiconductor element of the present invention can be a known or conventional molding method, and is not particularly limited. For example, the thermosetting resin composition of the present invention (reflector formation) And the like, and a method of subjecting the resin composition to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing.

  Specifically, for example, the thermosetting resin composition of the present invention (reflector forming resin composition) is injected into a predetermined mold (transfer molding mold, compression molding mold, etc.), and heat-cured. By doing so, a reflector can be formed. The heat curing conditions at this time can be appropriately selected from, for example, the conditions for forming the above-described cured product.

  The optical semiconductor device of the present invention can be obtained by using the optical semiconductor element mounting substrate of the present invention as the substrate of the optical semiconductor device and mounting the optical semiconductor element on the substrate.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device having at least the optical semiconductor element mounting substrate of the present invention and an optical semiconductor element mounted on the substrate. Since the optical semiconductor device of the present invention has a reflector formed of a cured product of the thermosetting resin composition of the present invention as a reflector, the light extraction efficiency is high, and the light intensity is less likely to decrease over time. Excellent in properties. FIG. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention. 2, 100 is a reflector, 102 is a metal wiring (lead frame), 103 is a bonding wire, 104 is a sealing material, 105 is a die bonding material, and 106 is an optical semiconductor element (LED element). In the optical semiconductor device shown in FIG. 2, since the light emitted from the optical semiconductor element 106 is reflected by the surface (reflection surface) of the reflector 100, the light from the optical semiconductor element 106 is extracted with high efficiency. As shown in FIG. 2, the optical semiconductor element in the optical semiconductor device of the present invention is usually sealed with a transparent sealing material (104 in FIG. 2).

  The thermosetting resin composition of the present invention is not limited to the use as the above-described reflector-forming resin composition. For example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite Used for various other applications such as materials, base materials, sheets, films, optical elements, optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc. Can do.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the unit of the compounding quantity of each component of the thermosetting resin composition in Table 1 is parts by weight.

Production Example 1
[Manufacture of epoxy resin]
134 g (1 mol) of trimethylolpropane, 1863 g (15 mol) of 4-vinylcyclohexene-1-oxide, and 31 g of boron trifluoride etherate were mixed at 60 ° C., and 4-vinylcyclohexene-1-oxide was analyzed by gas chromatography analysis. To obtain a resin having a vinyl group.
Further, 573 g of the resin obtained above was dissolved in ethyl acetate and charged into the reactor, and 387 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was kept at 40 ° C. After the completion of the peracetic acid preparation, the mixture was kept at 40 ° C. for 6 hours and aged. Thereafter, ethyl acetate was added to the reaction crude liquid, washed with alkaline water containing sodium carbonate, and then thoroughly washed with distilled water. Next, the ethyl acetate layer was concentrated to obtain an epoxy resin as a viscous transparent liquid. As a result of infrared absorption spectrum and ¹ H-NMR spectrum measurement, this epoxy resin is a trivalent group in which R ¹ in formula (1) is obtained by removing three hydroxyl groups from trimethylolpropane (ie, p is 3). It was confirmed that this was an epoxy resin. The weight average molecular weight in terms of standard polystyrene measured by GPC of this epoxy resin was 2800, and the epoxy equivalent was 180.
As a result of analysis by combustion ion chromatography, it was confirmed that the content of fluorine atoms in the epoxy resin obtained above was 5400 ppm (mg / kg).
(Combustion ion chromatography analysis conditions)
-Combustion conditions Equipment used: Product name "AQF-100" (Dia Instruments)
Sample: about 5mg
Combustion program: 2
Absorbent: H ₂ O ₂ (30 ppm)
Internal standard: Tartaric acid (5ppm)
Absorption liquid volume: 10ml
・ Ion chromatographic conditions Equipment used: Product name “DIONEX ICS-2000”
This column: AS-12
Precolumn: AG-12
Eluent: 2.70 mM Na ₂ CO ₃ + 0.3 mM EPM
Flow rate: 1.2 ml / min Detector: Conductivity detector Column temperature: 35 ° C
Injection volume: 100 μl

Example 1
As shown in Table 1, 100 parts by weight of the epoxy resin (EHPE3150) obtained in Production Example 1, 80 parts by weight of a curing agent (trade name “Ricacid MH-700G”, manufactured by Shin Nippon Rika Co., Ltd.), a curing accelerator (Trade name “U-CAT 5003”, manufactured by San Apro Co., Ltd.) 5 parts by weight, fluorine-based mold release agent (trade name “E-1630”, manufactured by Daikin Industries, Ltd.) 10 parts by weight, titanium oxide (trade name) 250 parts by weight of “White DCF-T-17007”, manufactured by Resino Color Industry Co., Ltd., 40 parts by weight of zinc oxide whisker (trade name “Panatetra WZ-0511”, manufactured by Amtec Co., Ltd.), and silica (trade name “ FB910 "(manufactured by Denki Kagaku Kogyo Co., Ltd.) 700 parts by weight was mixed at 90 ° C for 10 minutes using a planetary mixer, and the resulting mixture was cooled and pulverized. To obtain a thermosetting resin composition.

Examples 2-11, Comparative Examples 1-4
A powdery thermosetting resin composition was obtained in the same manner as in Example 1 except that the composition of the thermosetting resin composition was changed as shown in Table 1.

<Evaluation>
The following evaluation was implemented about the thermosetting resin composition obtained by the Example and the comparative example.

[Releasability (continuous moldability)]
Continuous molding was performed by a transfer molding machine using the thermosetting resin composition. In continuous molding, melamine resin (Nicarette manufactured by Nippon Carbide Industries Co., Ltd.) is molded into 8 shots at 180 ° C. for 120 sec and the mold is cleaned, then the mold release recovery material is molded into 180 ° C. for 90 sec 2 shots, and then 30 × 30 The continuous molding of the molded product with a thickness of 3 mm was performed at 180 ° C. for 90 sec. The sticking of the molded product to the mold during the continuous molding was observed, and the releasability (continuous moldability) was evaluated according to the following criteria. The results are shown in Table 1.
Sticking of the molded product occurs in less than 200 shots: × (deformability is poor)
No sticking of the molded product occurs even after 200 shots: ○ (Good releasability)

[Initial reflectance]
A test piece (cured product) having a thickness of 30 mm × 30 mm × 3 mm was molded using the thermosetting resin composition, and the reflectance of the test piece at a wavelength of 450 nm was measured using a spectrophotometer. Then, the initial reflectance was evaluated according to the following criteria. The results are shown in Table 1.
Measuring apparatus: Spectrophotometer UV-2450, manufactured by Shimadzu Corporation Reflectivity is less than 95%: × (low initial reflectance is poor)
Reflectivity is 95% or more: ○ (high initial reflectivity is good)

[Toughness]
Based on the ASTM # D5045, it was evaluated at room temperature of壊靭value K _1c. And toughness was evaluated according to the following criteria. The results are shown in Table 1.
K _1c is less than 3 MPa · m ^0.5 : × (poor toughness)
K _1c is 3 MPa · m ^0.5 or more: ○ (good toughness)

[Heat resistance and light resistance (yellowing resistance)]
-Heat resistance Using the same test piece (cured product; 30 mm x 30 mm x 3 mm thickness) as used in the evaluation of the initial reflectance, the test piece was placed in a dryer at 150 ° C for 500 hours, and then 450 nm The reflectance was measured at. And heat resistance was evaluated on the following reference | standard. The results are shown in Table 1.
Reflectance (reflectance after 500 hours at 150 ° C.) is less than 80%: x (poor heat resistance)
Reflectance (reflectance after 150 hours at 150 ° C.) is 80% or more: ○ (good heat resistance)
-Light resistance Using the same test piece (cured product; 30 mm x 30 mm x 3 mm thickness) as used in the evaluation of the initial reflectance, the test piece was subjected to a UV irradiation device (Daipura Winthes, Inc., Daipura Metal Weather Super Win) Mini) and irradiated with light at an illuminance of 18 mW / cm ² using a filter that cuts 400 nm or less while heating at 120 ° C. The sample was allowed to stand for 200 hours, and the reflectance was measured at 450 nm. And light resistance was evaluated on the following reference | standard. The results are shown in Table 1.
Reflectance (reflectance after light irradiation) is less than 90%: x (light resistance is poor)
Reflectivity (reflectance after light irradiation) is 90% or more: ○ (good light resistance)

[Comprehensive evaluation]
The case where all the above-mentioned evaluation results were (circle) (good) was made into comprehensive evaluation (circle) (excellent), and the case where any evaluation result was x (bad) was evaluated as comprehensive evaluation x (inferior).

  In Table 1, Celoxide 2021P represents the trade name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Corporation), and YX8034 represents the trade name “ YX8034 "(hydrogenated bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation).

DESCRIPTION OF SYMBOLS 100: Reflector 101: Metal wiring 102: Optical semiconductor element mounting area 103: Bonding wire 104: Sealing material of optical semiconductor element 105: Die bonding material 106: Optical semiconductor element

Claims (13)

An epoxy resin (A), a curing agent (B), a white pigment (C), and a whisker (D) are contained, and the epoxy resin (A) is represented by the following formula (1).

[In the formula (1), R ¹ represents a p-valent organic group. p shows the integer of 1-20. q shows the integer of 1-50, and the sum (total) of q in Formula (1) is an integer of 3-100. R ² represents any one of groups represented by the following formulas (1a) to (1c). However, at least one of R ^{2 in} the formula (1) is a group represented by the formula (1a).

[In Formula (1c), R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. ]]
A thermosetting resin composition characterized by being an epoxy resin represented by the formula:   The epoxy resin (A) opens 1,2-epoxy-4- (2-oxiranyl) cyclohexane with an organic compound having p hydroxyl groups in the molecule as an initiator in the presence of a cationic catalyst containing a fluorine atom. The thermosetting resin composition according to claim 1, which is an epoxy resin produced by polymerizing and then epoxidizing with an oxidizing agent.   The thermosetting resin composition according to claim 2, wherein the epoxy resin (A) contains 100 to 30000 ppm of fluorine atoms.   The thermosetting resin composition according to any one of claims 1 to 3, wherein the curing agent (B) is a liquid acid anhydride at 25 ° C.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide and silica.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the whisker (D) is at least one selected from the group consisting of zinc oxide whisker and titanium oxide whisker.   Furthermore, the thermosetting resin composition of any one of Claims 1-6 containing a fluorine-type mold release agent.   The thermosetting resin composition according to claim 7, wherein the fluorine-based release agent is an epoxy group-containing fluorine-substituted hydrocarbon.   It is a resin composition for transfer molding or compression molding, The thermosetting resin composition of any one of Claims 1-8.   It is a resin composition for reflector formation, The thermosetting resin composition of any one of Claims 1-9.   Hardened | cured material obtained by hardening the thermosetting resin composition of any one of Claims 1-10.   The board | substrate for optical semiconductor element mounting which has a reflector formed with the hardened | cured material of the thermosetting resin composition of Claim 10.   An optical semiconductor device comprising the optical semiconductor element mounting substrate according to claim 12 and an optical semiconductor element mounted on the substrate.

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