JP2009173763A - Thermosetting resin composition for sealing light emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition, which is colorless and transparent, gives a cured product with excellent heat resistance, light resistance, and moisture resistance, and is useful to a sealant for a light-emitting device (LED) emitting short-wavelength light, for sealing a light emitting element. <P>SOLUTION: The thermosetting resin composition for sealing a light emitting element includes a bisphenol-formaldehyde resin having a methylol group represented by a general formula 1, and an epoxy resin having two or more glycidyl groups in one molecule. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition for a light emitting device sealing material related to an optical semiconductor such as an LED or a CCD having excellent transparency, heat resistance, light resistance and moisture resistance.

  In recent years, light emitting devices such as optical semiconductors (LEDs) that have been put to practical use in various display boards, image reading light sources, traffic signals, large display units, and the like are mostly manufactured by resin sealing. As a sealing method, a transfer mold having advantages in terms of productivity and cost is used. In addition to the above-mentioned merit, the sealing resin used here is excellent in heat resistance and moisture resistance reliability. Therefore, aromatic epoxy resins and novolak type phenol resins and alicyclic acid anhydrides as curing agents are used. (For example, refer to Patent Document 1 and Patent Document 2).

  In addition, with the rapid progress of today's LEDs, higher output and shorter wavelengths of LED elements are rapidly becoming a reality. In particular, LEDs using nitride semiconductors emit light with a short wavelength and high output. Is being put to practical use. However, when LED elements using nitride semiconductors are encapsulated with novolac-type phenolic resins, the aromatic ring absorbs short-wavelength light, which causes deterioration of the encapsulated resin over time, resulting in light emission due to yellowing There arises a problem that the luminance is significantly reduced.

  Then, LED sealed using the alicyclic epoxy resin obtained by oxidizing a cyclic olefin is proposed (for example, refer patent document 3 and patent document 4). However, the cured products of these alicyclic epoxy resins are very brittle, are liable to cause cracking by the thermal cycle, and have extremely poor moisture resistance, so they are not suitable for applications requiring long-term reliability characteristics. .

  Therefore, an LED which is mainly composed of a hydrogenated bisphenol A type epoxy resin, blended with an alicyclic epoxy resin and a phosphorus antioxidant, and sealed with a methylhexahydrophthalic anhydride curing agent has been proposed (for example, , See Patent Document 5). However, this epoxy cured product is excellent in colorless transparency, but has the disadvantages of poor heat resistance and easy yellowing, so it is not suitable for LED device sealing applications that require heat resistance.

Furthermore, a method using a triazine derivative epoxy resin alone and an acid anhydride curing agent has also been proposed (see, for example, Patent Document 6). In this cured product, the heat resistance is improved, but because it is very brittle, it is easy to cause crack fracture by the thermal cycle similar to the one using the alicyclic epoxy resin, and the moisture resistance is extremely bad, It is not suitable for applications that require long-term reliability.
JP 2001-98143 A JP 2003-12774 A JP-A-9-213997 JP 2000-196151 A JP 2003-12896 A JP 2003-224305 A

  The present invention is colorless and transparent, can provide a cured product excellent in heat resistance, light resistance, and moisture resistance, and is particularly useful as a sealing material for LED emitting light having a short wavelength. It aims at providing a conductive resin composition.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, for a light emitting device sealing material containing a bisphenol-formaldehyde resin (A) having a methylol group represented by the following general formula (1) and an epoxy resin (B) having two or more glycidyl groups in one molecule. It is a thermosetting resin composition and its cured product.

[Wherein, R is a methylol group or hydrogen, each R may be different or the same, at least one of R is a methylol group, and X is CH ₂ , C (CH ₃ )] ₂ , S, SO ₂ , C (CF ₃ ) ₂ or O; n is an integer of 1 or more. ]

  The cured product of the thermosetting resin composition for a light emitting device sealing material of the present invention is excellent in colorless transparency, heat resistance, and moisture resistance, and also has excellent light resistance. It can be advantageously used as a thermosetting resin composition for a stopper.

Hereinafter, the present invention will be described in detail.
The bisphenol-formaldehyde resin (A) used in the thermosetting resin composition for a light emitting device sealing material of the present invention is represented by the above general formula (1). In the general formula (1), R is a methylol group or hydrogen, and each R may be different or the same, and at least one of R is a methylol group. A methylol group conventionally exerts an effect for inhibiting oxidation of a phenol skeleton that causes coloring due to oxidation. X is CH ₂ , C (CH ₃ ) ₂ , S, SO ₂ , C (CF ₃ ) ₂ or O, and n is an integer of 1 or more. For example, in the above general formula (1), a bisphenol A skeleton of X═C (CH ₃ ) ₂ , a bisphenol AF skeleton of X═C (CF ₃ ) ₂ , a bisphenol S skeleton of X═S, and X═CH ₂ Bisphenol F skeleton and the like are included. One or more of these may be included. Of these, bisphenol A and bisphenol AF are preferred from the viewpoint of curability.

  The weight average molecular weight of the bisphenol-formaldehyde resin (A) (hereinafter, the weight average molecular weight is abbreviated as Mw) is the viewpoint of curability, handleability, and toughness of the cured product of the thermosetting resin composition for light-emitting device sealing material. Therefore, it is preferably 400 or more, more preferably 500 to 2,000. When Mw is less than 400, sufficient viscosity cannot be obtained at the time of extrusion molding, and bubbles remain in the molded body. On the other hand, if it is greater than 2,000, the curing rate is high and sufficient fluidity cannot be obtained. Here, Mw can be measured by gel permeation chromatography (hereinafter gel permeation chromatography is abbreviated as GPC).

  The epoxy resin (B) used in the thermosetting resin composition for a light emitting device sealing material of the present invention is not particularly limited in its structure, molecular weight or the like, but is not colored, the light emitting device sealing material When the above three points are taken into consideration, the thermosetting resin composition for use has good fluidity at the time of molding, the bisphenol-formaldehyde and the epoxy resin form a crosslinked structure, and the softening point of the epoxy resin is low. In addition, it is desirable to have two or more glycidyl groups in one molecule.

  The compounding ratio of the bisphenol-formaldehyde resin (A) and the epoxy resin (B) is 70/30 to 30/70, preferably 65/35 to 35/65 as a mass ratio. If the blending ratio of bisphenol-formaldehyde resin (A) and epoxy resin (B) is not within the above range and there is a large amount of bisphenol-formaldehyde resin (A), the fluidity of the epoxy resin (B) is impaired and there is a risk of molding defects. There is. Moreover, when there are many epoxy resins (B), the effect which adds a bisphenol formaldehyde resin (A) is not fully exhibited, but there exists a possibility of hardening defect and coloring.

  The epoxy resin (B) used in the above is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, dicyclopentadiene- Phenol type epoxy resin, trisphenol type epoxy resin, tetramethylbiphenyl type epoxy compound, biphenol type epoxy compound, tetramethylbisphenol F type epoxy compound, aralkylphenol type epoxy resin, biphenylaralkylphenol type epoxy resin, bishydroxyfluorene type epoxy compound , Hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy, hydrogenated biphenol type epoxy resin, hydrogenated phenol Hydrogenated epoxy resins such as novolak type epoxy resins, hydrogenated cresol novolak type epoxy resins, hydrogenated bisphenol A novolak type epoxy resins, hydrogenated naphthalene diol type epoxy resins and hydrogenated phenol dicyclopentadiene novolak type epoxy resins, 3, 4 -Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,2-epoxy-vinylcyclohexene, bis (3,4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl-3,4-epoxycyclohexane, limonene Examples include diepoxide, 3,4-epoxycyclohexylmethanol, and dicyclopentadiene diepoxide. These may be used alone or in combination of two or more.

Moreover, it is more preferable that the thermosetting resin composition for a light emitting device sealing material of the present invention contains a thermosetting catalyst (C) from the viewpoint of curability. As the thermosetting catalyst (C), known catalysts such as imidazole, phosphine, and tertiary amine can be used. For example, phenylimidazole, 1-benzyl-2-methylimidazole 2-methylimidazole, triphenylphosphine, tolylylphosphine, methoxy-substituted triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra Phosphonium borate compounds such as naphthoyloxyborate, diazabicycloundecene, benzyldimethylamine and the like can be used. Among these, a phosphorus catalyst is particularly suitable. The amount of its use is 0.1-5 mass% with respect to all the epoxy components.
These may be used alone or in combination of two or more.

(Optional component)
The following components can be added and blended with the thermosetting resin composition for a light emitting device sealing material of the present invention as required.
(A) Powdery reinforcing agents and fillers; for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, and aluminum hydroxide Examples thereof include metal hydroxide, kaolin, mica, quartz powder, graphite, molybdenum disulfide and the like.
The component (a) is blended within a range that does not impair the transparency of the thermosetting resin composition for a light emitting device sealing material of the present invention, and is 100 parts by mass or less, for example, 10 parts with respect to 100 parts by mass of the resin component. -100 mass parts is suitable.

(B) Colorant or pigment; for example, titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes.
(C) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
(D) mold release agent; for example, naphthalene sulfonate (formal condensate of alkali metal (Na and K, etc., the same shall apply hereinafter), ammonium salt, etc.), polystyrene sulfonate (alkali metal salt, ammonium salt, etc.), Polyacrylate (alkali metal salt, ammonium salt, etc.), poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salt (alkali metal salt, ammonium salt, etc.), carboxymethyl cellulose, And polyvinyl alcohol, aliphatic alcohol (C4-30), alkyl (C1-30) phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide, aliphatic (C4-30) amine and aliphatic (C4-30) Alylene oxide such as amide (hereinafter, alkylene oxide is abbreviated as AO) .) (C2-4) adducts (1-30 moles), C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyhydric (2-6 or more) monoester compounds, C4-30 Alkali metal salts of fatty acids, sulfuric acid ester alkali metal salts of C4-30 aliphatic alcohols and AO (C2-4) 1-30 mol adducts of aliphatic alcohols, alkali metals of alkyl (C1-30) phenolsulfonic acids Salts, mono or diphosphate esters of C4-30 aliphatic alcohols and AO (C2-4) 1-30 mol adducts of aliphatic alcohols (alkali metal salts, quaternary ammonium salts, etc.), C4-30 Aliphatic amine hydrochloride, inorganic acid salt of monoester of triethanolamine and C4-30 fatty acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), C4-3 Quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl ammonium, dimethyl distearyl ammonium, etc.) inorganic acids include (hydrochloric, sulfuric, nitric and phosphoric acid, and the like) salts.
(E) Antifoaming agents; for example, C1-6 lower alcohols (methanol, butanol, etc.), C8-18 higher alcohols (octyl alcohol, hexadecyl alcohol, etc.), C10-20 higher fatty acids (oleic acid, stearic acid, etc.) ), Higher fatty acid ester of C11-30 (glycerin monolaurate), phosphate ester (tributyl phosphate, etc.), metal soap (calcium stearate, aluminum stearate, etc.), polyether (polyethylene glycol (hereinafter, polyethylene glycol is referred to as PEG) (Number average molecular weight (hereinafter abbreviated as Mn) 200 to 10,000), polypropylene glycol (Mn 200 to 10,000), etc.), silicone (dimethyl silicone oil, alkyl-modified silicone oil, full B silicone oil) and mineral oil (as silica powder was dispersed in mineral oil) and the like.
(F) Leveling agent; for example, PEG type nonionic surfactant (nonylphenol ethylene oxide (hereinafter, ethylene oxide is abbreviated as EO) 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct, etc.), polyhydric alcohol Type nonionic surfactant (sorbitan palmitate monoester, sorbitan stearate monoester, sorbitan stearate triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, Perfluoroalkyl betaine), modified silicone oil (polyether-modified silicone oil and (meth) acrylate-modified silicone oil), and the like.
(G) Silane coupling agent; amino group-containing silane coupling agent (γ-aminopropyltriethoxysilane, etc.), ureido group-containing silane coupling agent (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agent ( Vinyltriethoxysilane, etc.), methacrylate group-containing silane coupling agents (γ-methacryloxypropyltrimethoxysilane, etc.), epoxy group-containing silane coupling agents (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silanes Coupling agent (γ-isocyanatopropyltriethoxysilane etc.), polymer type silane coupling agent (polyethoxydimethylsiloxane etc.), cationic type silane coupling agent (N- (N-benzyl-β-aminoethyl) -γ- Aminopropyl Trimethoxysilane hydrochloride, etc.) and the like.
(H) Thixotropic imparting agent or thickener; for example, inorganic thixotropic imparting agent (bentonite, calcium carbonate, etc.) and organic thixotropic imparting agent (hydrogenated castor oil wax, calcium stearate, aluminum oleate, polymerized linseed oil, etc.) Is mentioned.
(I) slip agent; for example, higher fatty acid ester (butyl stearate, etc.), higher fatty acid amide (ethylene bis stearic acid amide, oleic acid amide, etc.), metal soap (calcium stearate, aluminum oleate, etc.), wax (paraffin wax, And polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.) and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil).
(J) antioxidants; for example, hindered phenol compounds (triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t -Butyl-4-hydroxybenzylphosphonate diethyl ester) and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
(K) UV absorber; for example, benzotriazole compound (2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.), triazine compound (2 -(4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol), benzophenone (2-hydroxy-4-n-octyloxybenzophenone, etc.), Shu And acid anilide compounds (2-ethoxy-2′-ethyloxalic acid bisanilide and the like).
When blending the above components (b) to (k), 30 parts by mass or less, for example, 0.01 to 30 parts by mass, preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the resin component. is there.

  When producing the thermosetting resin composition for a light emitting device sealing material of the present invention, it can be obtained by uniformly stirring and mixing the predetermined amount of the above components. At this time, various mixers, kneaders, rolls can be obtained. , Using an extruder or the like. In addition, there is no restriction | limiting in particular in the mixing | blending order of a component.

  The thermosetting resin composition for a light emitting device sealing material of the present invention can employ a potting method, a casting method, transfer molding, injection molding, and the like.

  There is no restriction | limiting in particular in the hardening method of the thermosetting resin composition for light emitting element sealing materials of this invention, Conventionally well-known hardening apparatuses, such as a closed-type hardening furnace and a tunnel furnace which can be continuously hardened, are employable. . The heating source is not particularly limited, and can be performed by a conventional method such as hot air circulation, infrared heating, high frequency heating or the like. The curing temperature and curing time are preferably in the range of 100 to 200 ° C. and 0.1 to 15 hours. After pre-reacting under conditions of 80 to 110 ° C. and 1 to 5 hours, the reaction is performed in a stepwise manner under the conditions of 120 to 180 ° C. and 1 to 10 hours, or 150 to 180 ° C., 1 to The reaction can be carried out at a high temperature for a short time under the condition of 5 hours.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this. In the following, parts represent parts by mass, and% represents mass%.

  In each Example and Comparative Example, the obtained cured resin was evaluated by the following method.

<Glass transition temperature Tg (° C.)>
The glass transition temperature was (Tg), and a test piece (width 2 mm × length 30 mm × thickness 1.0 mm) was prepared by transfer molding at 175 ° C. for 60 seconds and the resin composition was post-cured at 180 ° C. for 4 hours. The thing was measured in the range of 30 to 300 degreeC with the temperature increase rate of 10 degree-C / min using the viscoelasticity spectrometer (the Seiko Instruments make, DMS110).

<Initial YI value>
In accordance with JIS K7105, an initial YI value (Yellowness Index) after curing was measured.

<UV resistance>
Using a metering weather meter (manufactured by Suga Test Instruments Co., Ltd.), the YI value (Yellowness Index) of the cured product was measured after irradiation with ultraviolet rays at an irradiation intensity of 0.4 kW / m ² and a black panel temperature of 63 ° C. for 72 hours. .

<Heat resistance degradation>
The YI value (Yellowness Index) of the cured epoxy resin after heating at 150 ° C. for 72 hours was measured.

<Hygroscopic rate (%)>
In the hygroscopic test, a test piece (50 mmΦ × thickness 3.0 mm) was prepared by transfer molding at 175 ° C. for 60 seconds with a thermosetting resin composition and post-cured at 180 ° C. for 4 hours at 85 ° C. It was allowed to stand under the condition of 85% RH 168 hr, and the change in weight before and after moisture absorption was measured.

<Spectral transmittance>
A test piece (vertical 2 mm × width 2 mm × thickness 1.0 mm) was prepared by transfer molding at 175 ° C. for 60 seconds and post-cured at 180 ° C. for 4 hours to obtain “U” manufactured by Hitachi High-Technologies Corporation. -3300 ".

[Synthesis Example 1]
In a four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 500 parts of bisphenol A and 132 parts of a 50% formalin aqueous solution were blended, and 3.2 parts of trimethylamine was added while cooling to 30 ° C. or lower. The reaction was carried out at 2 ° C for 2 hours. After completion of the reaction, 2 parts of oxalic acid was added and stripped under reduced pressure at 100 ° C. and 400 mmHg for 2 hours to obtain a bisphenol A type bisphenol-formaldehyde resin (A1). Mw of (A1) was 1,500.

[Synthesis Example 2]
A four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was mixed with 736 parts of bisphenol AF, 263 parts of a 50% formalin aqueous solution and 220 parts of methyl isobutyl ketone, and trimethylamine 6.4 while cooling to 30 ° C. or lower. After adding the part, it was made to react at 100 degreeC for 2 hours. After completion of the reaction, 4 parts of oxalic acid was added and stripped under reduced pressure at 100 ° C. and 400 mmHg for 2 hours to obtain a bisphenol AF type bisphenol-formaldehyde resin (A2). Mw of (A2) was 900.

[Synthesis Example 3]
A four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was mixed with 548 parts of bisphenol S, 263 parts of a 50% formalin aqueous solution, and 164 parts of ethyl cellosolve, and 6.4 parts of trimethylamine while cooling to 30 ° C. or lower. After the addition, the mixture was reacted at 100 ° C. for 2 hours. After completion of the reaction, 4 parts of oxalic acid was added and stripped under reduced pressure at 100 ° C. and 400 mmHg for 2 hours to obtain a bisphenol S type bisphenol-formaldehyde resin (A3). Mw of (A3) was 1,200.

[Comparative Synthesis Example 1]
A four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was mixed with 456 parts of bisphenol A, 84 parts of a 50% formalin aqueous solution and 230 parts of methyl isobutyl ketone, and oxalic acid while cooling to 30 ° C. or lower. After adding 6 parts, it was made to react at 100 degreeC for 4 hours. After completion of the reaction, the temperature was raised in 2 hours while concentrating to 160 ° C., and a vacuum strip was performed at 160 ° C. and 100 mmHg for 30 minutes to obtain a bisphenol A type novolak resin (X1). Mw of (X1) was 900.

[Comparative Synthesis Example 2]
In a four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer, 500 parts of bisphenol S, 84 parts of 50% formalin aqueous solution and 250 parts of methyl isobutyl ketone are blended, and p-toluenesulfone is cooled to 30 ° C. or lower. After adding 2.5 parts of acid, the mixture was reacted at 100 ° C. for 4 hours. After completion of the reaction, 5.3 parts of 10% NaOH aqueous solution was added and neutralized, and then washed with 750 parts of pure water to remove neutralized salts. Next, the temperature was raised in 2 hours while concentrating to 160 ° C., and a vacuum strip was performed at 160 ° C. and 100 mmHg for 30 minutes to obtain a bisphenol S type novolak resin (X2). The Mw of (X2) was 1,100.

Examples 1-3 and Comparative Examples 1-2
Table 1 shows the composition of the thermosetting resin composition for light-emitting element sealing material, and Table 2 shows the physical property evaluation results. Using the thermosetting resin composition for a light emitting device sealing material obtained by blending, stirring and dissolving each component shown in the composition composition column of Table 1, a mold suitable for each test item by transfer molding, and Created under curing conditions.

Epicoat 828: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
Denacol EX-201: Resorcinol type epoxy resin (manufactured by Nagase ChemteX Corporation)
EOCN-102S: Orthocresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
NC-3000H: biphenylaralkylphenol type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
IRGAFOS 168: Antioxidant (Ciba Specialty Chemicals)
IRGNOX 1010: Antioxidant (Ciba Specialty Chemicals)
Neutron-2: Stearic acid amide release agent (manufactured by Nippon Seika Co., Ltd.)

  Comparative Examples 1 and 2 have a high initial YI, and it can be seen that the YI value is further increased by ultraviolet irradiation for a long time, resulting in ultraviolet degradation. In addition, it can be seen that the YI value changes greatly even in a high temperature environment, and the heat deterioration due to oxidation is increased. On the other hand, Examples 1 to 4 have low initial YI, and it can be seen that good transparency can be obtained with little UV deterioration due to UV irradiation and less heat deterioration under high temperature environment.

  The thermosetting resin composition for optical materials of the present invention is excellent in light resistance, heat resistance, and moisture resistance, and is extremely useful for light emitting device sealing materials related to optical semiconductors such as LEDs and CCDs.

Claims (4)

The heat | fever for light emitting element sealing materials containing the bisphenol formaldehyde resin (A) which has the methylol group represented by following General formula (1), and the epoxy resin (B) which has a 2 or more glycidyl group in 1 molecule. Curable resin composition.

[Wherein, R is a methylol group or hydrogen, each R may be different or the same, at least one of R is a methylol group, and X is CH ₂ , C (CH ₃ )] ₂ , S, SO ₂ , C (CF ₃ ) ₂ or O; n is an integer of 1 or more. ]   The thermosetting resin composition for a light emitting device sealing material according to claim 1, wherein the bisphenol-formaldehyde resin (A) is one or more selected from the above general formula (1).   The compounding ratio of bisphenol-formaldehyde resin (A) and epoxy resin (B) is 70 / 30-30 / 70 as mass ratio, The thermosetting for light emitting element sealing materials of any one of Claims 1-2 Resin composition.   Hardened | cured material formed by hardening the thermosetting resin composition for light emitting element sealing materials of any one of Claims 1-3.