JP2007039522A - Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product - Google Patents

Abstract

A thermosetting resin composition that provides a cured product excellent in both ultraviolet resistance and heat resistance, and a light-emitting diode using the composition as a sealing material.
A thermosetting resin composition comprising cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester and hydrogenated trimellitic anhydride and no special curing accelerator. And a light emitting diode using the composition as a sealing material.

Description

  The present invention relates to a thermosetting resin composition, a translucent cured product obtained by thermosetting the composition, and a light-emitting diode sealed with the cured product.

In recent years, blue or ultraviolet light emitting diodes having an emission wavelength of 350 nm to 550 nm have been obtained with high brightness using GaN-based compound semiconductors such as GaN, GaAlN, InGaN, and InAlGaN. White light emitting diodes combining diodes and phosphors have also been put into practical use.
The sealing resin for these short wavelength light emitting diodes is required to have high transmittance from blue light to ultraviolet light and that the transmittance does not decrease due to heat generated during operation or short wavelength light from the light emitting diode chip. Yes. Bisphenol-based epoxy transparent resins using acid anhydride-based curing agents that have been widely used as sealing materials or molding materials for light-emitting elements of red and green light-emitting diodes have high adhesiveness and mechanical durability. However, since the light transmittance with respect to the light of a short wavelength is low, it had the fault that light resistance is low, or it colors by light deterioration or heat deterioration.

  Therefore, a resin composition containing a non-aromatic epoxy resin as an active ingredient has been proposed as a resin composition for encapsulating a short wavelength light emitting diode, specifically, 3,4-epoxycyclohexylmethyl-3,4-epoxy. Light-emitting diode encapsulating resin composition containing cyclohexanecarboxylate and methylhexahydrophthalic anhydride as active ingredients (Patent Document 1), hydrogenated bisphenol A type epoxy resin and methylhexahydrophthalic anhydride as main components A resin composition for sealing a light emitting diode (Patent Documents 1 and 2) and the like are disclosed. Epoxy resin cured products mainly composed of these non-aromatic epoxy resins and cured with alicyclic carboxylic acid anhydrides have a long period of time because the carbon-carbon double bonds that cause photodegradation are hardly present in the polymer. A relatively good visible light transmittance can be maintained even after the light irradiation.

  However, in surface-mounted light-emitting diodes (in which light-emitting elements are directly mounted on the substrate surface), the demand for which is increasing in recent years, it is necessary to form a sealing resin in a thin film, but acid anhydride curing agents are volatile and Because of its high hygroscopicity and slow curing speed, when applied to a surface-mounted light emitting diode, the properties of the cured product may fluctuate due to the effects of volatilization and moisture absorption, and a sufficient sealing effect may not be obtained. Use of curable epoxy resin may be avoided.

  In such a case, a cationic curing agent such as an aromatic sulfonium salt is used instead of the acid anhydride curing agent. Cationic curing agents have low volatility and induce rapid epoxy resin curing compared to acid anhydride curing agents. However, many cationic curing agents have a carbon-carbon double bond such as an aromatic ring as the basic skeleton of the molecule, and they easily absorb light of short wavelengths below blue and are thermally unstable. It is. That is, a cured product obtained with a cationic curing agent is likely to be yellowed under irradiation with light having a short wavelength or under high temperature. In addition, epoxy resin cured products with a cationic curing agent have poor flexibility, and when such a resin is used as a sealing material for a light emitting diode, a large stress is generated between the light emitting element and the sealing resin during heating or cooling. Arise. This stress induces the occurrence of resin cracks, peeling of the sealing resin from the base material, cutting of the bonding wire, and the like, which causes a decrease in output and failure of the light emitting diode.

Therefore, the present inventors have described the heat stability of a transparent resin composition comprising a non-aromatic epoxy resin and an alicyclic carboxylic acid anhydride that gives a relatively good thermoset compared to a cationically cured epoxy resin. Examination revealed that the cured product of the composition was transparent immediately after curing but was already slightly colored and had a problem of further coloring when stored at high temperature (150 ° C.). .
JP 2000-196151 A JP 2003-073452 A JP 2003-012896 A

  Recently, the application as a power LED used as a light source is spreading by passing a larger amount of current through the light emitting element to obtain higher luminance. Although the luminous efficiency of the LED is remarkably improved, the energy that is discarded as heat is still large. In particular, the resin that seals the power LED is required to have higher heat stability. Accordingly, an object of the present invention is to provide a cured product that can maintain excellent light transmittance even when it is exposed to blue light / ultraviolet light for a long time or used at a high temperature for a long time. It is providing the thermosetting resin composition which gives the hardened | cured material which is excellent in all.

  In order to achieve the above-mentioned object, the present inventors have intensively studied combinations of various epoxy resins having no carbon-carbon double bond and various acid anhydride curing agents in consideration of ultraviolet resistance and heat resistance. did. As a result, a composition containing cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester as the main component of the epoxy resin fraction and hydrogenated trimellitic anhydride as the main component of the acid anhydride-based curing agent fraction The present invention was completed by finding that a thermoset of the product exhibits remarkable heat stability.

Therefore, the present invention contains cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the following formula (1) as an epoxy resin component, and the following formula (2) as an acid anhydride-based curing agent component. The thermosetting resin composition containing the hydrogenated trimellitic anhydride represented by these is provided.

  In the composition of the present invention, the content of the hydrogenated trimellitic anhydride represented by the formula (2) is preferably 10 to 100 with respect to the entire acid anhydride-based curing agent component contained in the composition. % By weight, more preferably 25 to 100% by weight, still more preferably 50 to 100% by weight.

  In the composition of the present invention, the content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the formula (1) is preferably relative to the entire epoxy resin component contained in the composition. Is 33 to 100% by weight, more preferably 50 to 100% by weight, and still more preferably 67 to 100% by weight.

Moreover, this invention provides the translucent resin hardened | cured material obtained by hardening | curing said thermosetting resin composition of this invention.
Furthermore, this invention provides the light emitting diode by which the light emitting element is sealed by the translucent resin cured material of said invention. The light emitting diode of the present invention preferably has a main light emission peak wavelength of 550 nm or less.
In addition, the present invention provides the thermosetting property of the present invention, further comprising a fluorescent material capable of emitting fluorescence by absorbing at least a part of light emitted from a light emitting device having a main emission peak wavelength of 550 nm or less. Provided is a light-emitting diode in which a light-emitting element is sealed with a light-transmitting resin cured product obtained by curing a resin composition.

  According to the present invention, it is possible to provide a thermosetting resin composition that gives a cured resin product excellent in both ultraviolet resistance and heat stability, and a light-emitting diode using the cured product as a sealing material, Further, since the thermosetting resin composition has a sufficient curing rate, it can be suitably used for a surface-mounted light emitting diode.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the above formula (1) as an epoxy resin component, and the above formula as an acid anhydride curing agent component. It is a thermosetting resin composition epoxy resin characterized by containing the hydrogenated trimellitic anhydride represented by (2), and has a sufficient curing speed even if it contains substantially no curing accelerator. Further, it is characterized by providing a cured product having excellent ultraviolet resistance and heat resistance.

Hereinafter, each component of the thermosetting resin composition of the present invention will be described.
The thermosetting resin composition of this invention contains the hydrogenated trimellitic anhydride represented by the said Formula (1) as an acid anhydride type hardening | curing agent component.
Usually, an acid anhydride-curing type epoxy resin composition includes an epoxy resin, a carboxylic acid anhydride (including a chemical equivalent of about 1 in terms of stoichiometric ratio with the resin), a curing accelerator (an epoxy resin weight of about 0.00 to (Including several percent) and various additives added as necessary. Among these components, the curing accelerator greatly affects the ultraviolet resistance and heat stability of the cured product. Curing accelerators and curing initiators are chemically unstable and are a major cause of yellowing due to ultraviolet rays and heat in the resulting cured product. Actually, the ultraviolet resistance and heat stability of a cured product obtained by thermosetting in the presence of various curing accelerators with a constant epoxy resin component and an acid anhydride component vary greatly depending on the type of the curing accelerator. In particular, when an amine-based or imidazole-based curing accelerator is used, serious coloring may occur. Although there are compositions that can be thermally cured even in the absence of a curing accelerator, generally, heating for a long time is required. Many of the acid anhydrides used as curing agents are highly volatile and hygroscopic, and the composition changes with time due to prolonged heating, which leads to poor curing and lot-to-lot variations in resin properties.

  On the other hand, the hydrogenated trimellitic anhydride, which is an essential component in the resin composition of the present invention, has a self-catalytic ability (spontaneous curing promoting ability) for curing an epoxy resin, and a curing accelerator exists. A curing rate equal to or higher than the case is given. Since a curing accelerator that adversely affects the ultraviolet resistance and heat stability of the cured product is not required, these characteristics are greatly improved by blending the hydrogenated trimellitic anhydride. Moreover, although hydrogenated trimellitic anhydride has hygroscopicity, it has almost no volatility, and can reduce the variation factor of cured product characteristics.

  The content of hydrogenated trimellitic anhydride is preferably 10 to 100%, more preferably 25 to 100%, and still more preferably 50 to 100% by weight percent with respect to the whole acid anhydride curing agent component. If the content of hydrogenated trimellitic anhydride is less than 10% of the acid anhydride-based curing agent component, the self-catalytic ability (self-curing promoting ability) exhibited by the above-mentioned hydrogenated trimellitic anhydride is difficult to be exhibited and good. Hard to be cured. Although it depends on the coexisting acid anhydride, 50% or more of hydrogenated trimellitic acid anhydride should be used in order to substantially suppress the resin viquet (resin volume decrease due to volatilization of the acid anhydride) associated with thermosetting. It is desirable to contain. The resin composition of the present invention having such a hydrogenated trimellitic anhydride content can also be applied to sealing of surface-mounted light emitting diodes.

  The acid anhydride used together with the hydrogenated trimellitic anhydride is not particularly limited as long as the desired effect of the present invention is obtained, and aliphatic acid anhydrides such as polyazeline acid anhydride, dodecenyl succinic anhydride, etc. Alicyclic acid anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic acid (methanotetrahydrophthalic acid), methyl nadic anhydride, Aromatic acid anhydrides such as bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid anhydride, For example, halogenated acid anhydrides such as trimetic anhydride, pyromellitic anhydride, etc. Such as phthalic anhydride and the like.

  In view of UV resistance, those containing no carbon-carbon double bond are preferred, and preferred acid anhydrides include hexahydrophthalic anhydride and methylhexahydrophthalic anhydride represented by the following formulas (3) to (6). And the like. However, it may be preferable to supplement a small amount of an acid anhydride having a carbon-carbon double bond as long as the durability required as a sealing resin is not impaired. For example, by diluting the hydrogenated trimellitic anhydride to some extent with a low-viscosity liquid acid anhydride, the viscosity of the resin composition of the present invention is lowered and the handling difficulty derived from the hydrogenated trimellitic anhydride is remarkably improved. can do.

（式中、Ｍｅはメチル基を表す） These acid anhydrides can be used alone or in combination of two or more.

(In the formula, Me represents a methyl group)

The thermosetting resin composition of the present invention contains cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the above formula (1) as an essential component as an epoxy resin component.
The ultraviolet resistance of the acid anhydride curable epoxy resin depends not only on the acid anhydride but also on the epoxy resin component. Examples of the epoxy resin having excellent ultraviolet resistance include various alicyclic epoxy resins, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, epoxy-modified tetramethyldisiloxane, cyclohexane-1,2,4- Examples thereof include tricarboxylic acid triglycidyl ester. Therefore, the present inventors have intensively studied the resin physical properties of a stoichiometric mixture of each of these epoxy resins and hydrogenated trimellitic anhydride. As a result, it was confirmed that the use of hydrogenated trimellitic anhydride as a curing agent improved the ultraviolet resistance and heat stability of each epoxy resin. Cyclohexane-1,2,4 -It has been found that the heat-resistant stability of a cured product obtained from a composition containing triglycidyl tricarboxylic acid ester and hydrogenated trimellitic anhydride is extremely high.

  Regarding the content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester in the epoxy resin component contained in the thermosetting resin composition of the present invention, from the viewpoint of improving the heat resistance stability, The higher the xylene-1,2,4-tricarboxylic acid triglycidyl ester content, the better the results, and the cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester content is weight percent based on the total epoxy resin component. And preferably 33 to 100%, more preferably 50 to 100%, still more preferably 67 to 100%. When the content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester in the epoxy resin component is less than 33%, the effect of improving the heat stability can be obtained by using hydrogenated trimellitic anhydride as a curing agent. Hateful. However, in order to satisfy other required characteristics (flexibility, toughness, etc.) required for the sealing resin of the light emitting diode, it may be preferable to dilute with a different kind of epoxy resin component or resin modifier. As long as the desired effect is obtained, different types of epoxy resin components can be added.

As a preferable epoxy resin component that can be used together with cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester, various epoxy resins excellent in ultraviolet resistance, such as alicyclic epoxy resins, aliphatic epoxy resins, Examples include hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, and epoxy-modified tetramethyldisiloxane, but are not limited thereto.
Moreover, you may contain the epoxy resin which has a small amount of carbon-carbon double bonds in the range which does not impair the durability requested | required as sealing resin. These epoxy resin components can be used alone or in combination of two or more. Furthermore, an oxetane resin copolymerizable with an epoxy resin or various modified resins may be used.

  Although the said acid anhydride hardening | curing agent in the thermosetting resin composition of this invention should just be contained about the stoichiometric amount with respect to an epoxy resin component, Preferably it is 0.4-1 with respect to 1 equivalent of epoxy resin components. It is about 2 equivalents, preferably about 0.5 to 1.0 equivalents. Furthermore, the content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester and hydrogenated trimellitic anhydride in the acid anhydride curing agent and epoxy resin component can be selected from the above ranges, respectively. The degree of the effect due to the addition of these components can be adjusted, and by adjusting the content of both, a cured resin product having various characteristics according to the content of both can be obtained.

  An object of the present invention is to provide a thermosetting resin composition having excellent ultraviolet resistance and heat stability and satisfying mechanical properties required for a sealing resin for a light emitting diode, and the composition as a sealing material. It is to provide a light emitting diode. Therefore, as long as the object of the present invention is achieved, the thermosetting resin composition of the present invention includes a phosphor for color conversion, an inorganic filler, an antioxidant, a light stabilizer, a resin modifier, and a silane coupling agent. One or more of various additives such as

  In order to further improve the heat stability of the cured product obtained from the thermosetting resin composition of the present invention, it is preferable to contain an antioxidant as an additive in the composition. Examples of the antioxidant include phenolic antioxidants (such as BHT), sulfur-based antioxidants (such as mercaptopropionic acid derivatives), and phosphorus-based antioxidants (such as HCA). Among these, a phenolic antioxidant can be suitably used, and more preferably, a phenolic antioxidant and a relatively small amount of a sulfur-based antioxidant can be used in combination.

  As content of the phenolic antioxidant in the resin composition of this invention, it is about 0.1-4 weight part normally with respect to a total of 100 weight part of a composition component, Preferably it is 0.2-2 weight About 1 part, more preferably about 0.5 to 1 part by weight. When using a sulfur type antioxidant together, it is preferable to make the content into about 0.1 weight part or less with respect to a total of 100 weight part of a composition component.

  The present invention also provides a translucent resin cured product obtained by curing the thermosetting resin composition of the present invention. The thermosetting resin composition of the present invention can be cured by a method usually used for acid anhydride curable epoxy resins to obtain a cured resin. The translucent resin cured product of the present invention is extremely excellent in UV resistance and heat stability due to the constitution of the thermosetting resin composition of the present invention in combination with a specific epoxy resin component and a specific acid anhydride. Therefore, it can be suitably used for a surface-mount type light emitting diode.

The present invention further provides a light-emitting diode in which the light-emitting element is sealed with the light-transmitting resin cured product of the present invention. The light-transmitting resin cured product of the present invention is excellent in ultraviolet resistance and heat stability, has little coloring, and has extremely excellent light-transmitting properties. Therefore, blue light emission and ultraviolet light emission with an emission wavelength of 550 nm or less. It can be suitably used as a sealing resin for short wavelength light emitting diodes.
In particular, in the case of a surface mount type light emitting diode of a type that is directly mounted on the surface of a printed circuit board by solder bonding or the like, the amount of the light-transmitting resin cured material that seals the light emitting element is two connection terminals. Is smaller than the so-called shell-hole type (or Through-hole type) extending from the light-transmitting resin cured product, and the distance from the light emitting element surface to the surface of the light-transmitting resin cured material is short. Therefore, even when the transparent resin cured product is formed thinly, sufficient sealing can be obtained and it can be used preferably.

  In addition, the thermosetting resin composition can be a fluorescent substance capable of emitting fluorescence by absorbing at least a part of light emitted from a light emitting element, particularly preferably a light emitting element having a main emission peak wavelength of 550 nm or less. Is added as a sealing material for the light emitting element, whereby a color conversion type light emitting diode including the light emitting element can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to the Example shown below.

[Example 1]
Mitsubishi Gas Chemical Co., Ltd. hydrogenated trimellitic anhydride (HTAn; mixed as 1.5 functional) and Sakamoto Yakuhin's EPP25 (formula (1) cyclohexane-1,2,4-tricarboxylate triglycidyl Ester; trifunctional) was weighed so that the stoichiometric ratio was approximately 0.5, and preheated to 80 ° C. was thoroughly stirred and mixed to obtain a fluid resin composition. Next, the resin composition was poured into a resin shaping mold for producing a resin plate having a thickness of 2 mm, and heat curing treatment was performed at 120 ° C. for 1 hour and 150 ° C. for 3 hours to obtain a colorless product having a thickness of 2 mm. A transparent resin plate was obtained.

[Example 2]
0.5 parts by weight of BHT was added to 100 parts by weight of the resin composition described in Example 1, and a colorless transparent resin plate having a thickness of 2 mm was obtained as a cured product by the same procedure as in Example 1.

[Comparative Example 1]
Instead of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester described in Example 1, hydrogenated bisphenol A diglycidyl ether (YX8000; bifunctional) of Japan Epoxy Resin Co., Ltd. was used. In the same manner as in No. 1, a 2 mm thick resin plate having a very slightly yellow color was obtained as a cured product.

[Comparative Example 2]
In place of the cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester described in Example 1, Daicel Chemical Industries, Ltd. alicyclic epoxy resin, Celoxide 2021P (3,4-epoxycyclohexenylmethyl- Using a 3 ′, 4′-epoxycyclohexene carboxylate; bifunctional), a colorless and transparent resin plate having a thickness of 2 mm was obtained as a cured product in the same procedure as in Example 1.

[Comparative Example 3]
Instead of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester described in Example 1, alicyclic epoxy resin ERLX-4360 (formula (7); bifunctional) of Dow Chemical Company was used. In the same procedure as in Example 1, a colorless transparent resin plate having a thickness of 2 mm was obtained as a cured product.

（式中、Ｍｅはメチル基を表す） [Comparative Example 4]
Instead of the cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester described in Example 1, an alicyclic epoxy-modified tetramethyldisiloxane (formula (8), BEP-SI2; manufactured by Toagosei Co., Ltd .; In the same procedure as in Example 1, a resin plate having a very slightly yellow color with a thickness of 2 mm was obtained.

(In the formula, Me represents a methyl group)

[Comparative Example 5]
Methylhexahydrophthalic anhydride (MH-700; monofunctional) from Shin Nippon Rika Co., Ltd. and EPP25 from Sakamoto Pharmaceutical Co., Ltd. (cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester of formula (1); Trifunctional) and an organic phosphonium salt compound epoxy curing catalyst, Hishikorin PX-4ET manufactured by Nippon Chemical Industry Co., Ltd. with respect to 100 parts by weight as a whole. What added 2 weight part as a hardening accelerator was well stirred and mixed, and the fluid resin composition was obtained. Thereafter, a resin plate having a very slightly yellow color with a thickness of 2 mm was obtained as a cured product by the same procedure as in Example 1.

[Comparative Example 6]
Instead of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester described in Comparative Example 5, hydrogenated bisphenol A diglycidyl ether (YX8000) of Japan Epoxy Resin Co., Ltd. was used, and the same as Comparative Example 5 According to the procedure, a resin plate having a slightly yellow color with a thickness of 2 mm was obtained as a cured product.

[Comparative Example 7]
Instead of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester described in Comparative Example 5, Daicel Chemical Industries, Ltd. alicyclic epoxy resin, Celoxide 2021P was used, and the same procedure as Comparative Example 5 was used. As a cured product, a 2 mm thick resin plate having a very slightly yellow color was obtained.

  A part was cut out from each of the resin plates obtained in Examples 1 and 2 and Comparative Examples 1 to 7 to make samples, and UV resistance tests and heat stability tests shown in the following (1) and (2) were performed. It was.

(1) Ultraviolet resistance test Light from the SP-V ultra-high pressure mercury lamp manufactured by USHIO ELECTRIC CO., LTD. The UV resistance of the sample was evaluated by the time until the change was recognized. The light illuminance on the sample irradiation surface was 5000 mW / cm ² and the spot diameter was 5 mm. The atmospheric temperature at the time of evaluation was set to 60 ° C.
Evaluation criteria ◎:> 100 hours ○: 50-100 hours △: 5-50 hours ×: <5 hours

(2) Heat stability test
The degree of yellowing after the resin plate sample was left in an electric drying oven at 180 ° C. for 48 hours was visually evaluated to evaluate the heat stability of the sample.
Evaluation criteria ◎: No change ○: Slight coloration △: Yellowing ×: Strong yellowing (browning)

The following table shows the evaluation results from Example 1 to Comparative Example 7.

  As is clear from the results shown in the above table, the cured product provided by the thermosetting resin composition of the present invention is excellent in both ultraviolet resistance and heat stability, and particularly contains an optimal amount of a phenolic antioxidant. The cured product (Example 2) has heat-resistant stability that is notable as an epoxy resin.

[Example 3]
26 parts by weight of hydrogenated trimellitic anhydride (formula (2), HTMan) from Mitsubishi Gas Chemical Co., Ltd., EPP25 from Sakamoto Yakuhin Kogyo Co., Ltd. 37 parts by weight of glycidyl ester), 37 parts by weight of Celite 2021P from Daicel Chemical Industries, Ltd., and 0.5 parts by weight of phenolic antioxidant BHT were each weighed and mixed premixed at 80 ° C. with sufficient agitation. A resin composition was obtained. Next, the resin composition was poured into a package of a resin-shaped mold for producing a resin plate having a thickness of 2 mm and a surface-mounted light-emitting diode disposed on a lead frame, and 120 ° C. × 1 hour and 150 ° C. × 3 A time-hardening treatment was applied to obtain a colorless and transparent cured product. Using the obtained resin plate and lead frame sample (surface mounted LED), the ultraviolet resistance test and heat stability test of (1) and (2) above, and the heat shock resistance of (3) and (4) below Tests and volume reduction evaluation tests were conducted. The evaluation results were all the highest evaluation ◎ in tests (1) to (3), and the evaluation ◯ in test (4).

(3) Heat shock resistance test
The heat shock cycle of 30 minutes exposure at -40 ° C. and 120 ° C. was repeated, and the heat shock resistance of the sample was evaluated by the number of cycles in which lead cracking was first observed in the lead frame sample.
Evaluation criteria ◎:> 150 times ○: 50 to 150 times △: 5 to 50 times ×: <5 times

(4) Volume reduction degree evaluation test The lead frame sample was filled with the pre-curing resin composition until the opening became a flat surface, and the presence or absence of depression of the resin surface due to the volume reduction when it was cured was visually evaluated. .
Evaluation criteria ○: Volume reduction / no depression ×: Volume reduction / concave

Claims (13)

It contains cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the following formula (1) as an epoxy resin component, and hydrogen represented by the following formula (2) as an acid anhydride-based curing agent component. A thermosetting resin composition containing an added trimellitic anhydride.

  2. The heat according to claim 1, wherein the content of the hydrogenated trimellitic anhydride represented by the formula (2) is 10 to 100 wt% with respect to the entire acid anhydride curing agent component contained in the composition. Curable resin composition.   The heat according to claim 2, wherein the content of the hydrogenated trimellitic anhydride represented by the formula (2) is 25 to 100% by weight with respect to the entire acid anhydride-based curing agent component contained in the composition. Curable resin composition.   The heat according to claim 3, wherein the content of the hydrogenated trimellitic anhydride represented by the formula (2) is 50 to 100% by weight with respect to the entire acid anhydride curing agent component contained in the composition. Curable resin composition.   2. The content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the formula (1) is 33 to 100% by weight based on the whole epoxy resin component contained in the composition. The thermosetting resin composition in any one of -4.   The content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the formula (1) is 50 to 100% by weight based on the whole epoxy resin component contained in the composition. The thermosetting resin composition described in 1.   7. The content of cyclohexane-1,2,4-tricarboxylic acid triglycidyl ester represented by the formula (1) is 67 to 100% by weight based on the whole epoxy resin component contained in the composition. The thermosetting resin composition described in 1.   The thermosetting according to any one of claims 1 to 7, comprising a fluorescent material capable of emitting fluorescence by absorbing at least part of light emitted from a light emitting device having a main emission peak wavelength of 550 nm or less. Resin composition.   A translucent resin cured product obtained by curing the thermosetting resin composition according to claim 1.   A translucent resin cured product obtained by curing the thermosetting resin composition according to claim 8.   A light-emitting diode, wherein the light-emitting element is sealed with the light-transmitting resin cured product according to claim 9.   The light emitting diode according to claim 11, wherein the main light emission peak wavelength of the light emitting element is 550 nm or less. 11. A light emitting diode, wherein the light emitting element has a main emission peak wavelength of 550 nm or less, and the light emitting element is sealed with the light-transmitting resin cured product according to claim 10.