WO2014010420A1 - Resin composition, cured product thereof, and optical semiconductor device using same - Google Patents

Abstract

A resin composition obtained by blending at least an epoxy compound, an acid anhydride, a curing accelerator, and a polyvalent alcohol, wherein the epoxy compound is selected from the group consisting of compounds represented by formula (1-1), compounds represented by formula (1-2), compounds represented by formula (1-3), and compounds represented by formula (1-4), and the blended amount of the polyvalent alcohol is 2 to 30 parts by mass in relation to 100 parts by mass of the acid anhydride.

Description

Resin composition, cured product thereof and optical semiconductor device using the same

The present invention relates to a resin composition containing an epoxy compound, a cured product thereof, and an optical semiconductor device using the same.

In recent years, most of optical semiconductor devices such as light emitting diodes and light receiving elements such as light emitting diodes (LEDs) that have been put to practical use in various display boards, light sources for image reading, traffic signals, large display units, etc. are mostly sealed. Manufactured using resin. As such a sealing resin, an epoxy resin is generally used because of its excellent heat resistance, adhesiveness, moisture resistance, mechanical strength, electrical characteristics, and the like.

Conventionally, bisphenol-based diglycidyl ether and phenol-based novolak-type epoxy resins have been generally used as sealing materials. However, when nitride LEDs having a light emission wavelength in the blue to near-ultraviolet region that have been put into practical use in recent years are sealed with these conventional epoxy resins, the aromatic ring of the epoxy resin absorbs short-wavelength light. Causes a problem that the light emission intensity of the LED is significantly reduced. In order to suppress such deterioration due to light and heat, alicyclic epoxy resins that are less likely to deteriorate due to light and heat have been put into practical use.

On the other hand, the epoxy resin composition using such an alicyclic epoxy resin has a drawback that the obtained cured product has poor toughness and easily cracks due to changes in conditions such as temperature. In order to solve this problem, as a method for toughening a cured product obtained from an epoxy resin composition, a method using a modifier composed of various polymers is known.

For example, Patent Document 1 proposes an improvement in flexibility by using an epoxy resin curing agent obtained by bonding a vinylidene double bond at a terminal of a butene polymer and an unsaturated acid anhydride by an addition reaction. Yes.

Further, Patent Document 2 proposes a method in which an alkyl group-containing dicarboxylic acid is used as a curing agent.

By the way, conventionally, it is known that tetrahydroindene is by-produced when vinylnorbornene is synthesized by reaction of cyclopentadiene with 1,3-butadiene. In recent years, there has been a demand for effective use of tetrahydroindene. For example, Patent Document 3 discloses a method for producing a diepoxide of tetrahydroindene, which is an epoxy compound having two alicyclic skeletons in a molecule, from tetrahydroindene.

In Patent Document 4, as a substitute for a glass substrate, (A) a non-ester type alicyclic epoxy compound, (B) an epoxy compound different from the above (A), and (C) a cationic polymerization initiator are blended in predetermined amounts. The use of a thermosetting resin composition is disclosed, and a diepoxide of tetrahydroindene is exemplified as the (A) non-ester type alicyclic epoxy compound.

JP 2002-069153 A JP 2011-057617 A JP 2004-182648 A JP 2005-068303 A

The present invention is a resin composition capable of obtaining a cured resin product having excellent flexibility and impact resistance, and capable of realizing an appropriate viscosity with good workability such as casting work. The purpose is to provide. Another object of the present invention is to provide a cured resin obtained by curing the resin composition and an optical semiconductor device sealed using the resin composition.

The present invention is a resin composition comprising at least an epoxy compound, an acid anhydride, a curing accelerator and a polyhydric alcohol, wherein the epoxy compound is a compound represented by the following formula (1-1), An epoxy compound selected from the group consisting of a compound represented by the formula (1-2), a compound represented by the following formula (1-3), and a compound represented by the following formula (1-4), The present invention relates to a resin composition in which the blending amount of the polyhydric alcohol is 2 to 30 parts by mass with respect to 100 parts by mass of the acid anhydride.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or The alkoxy group which may have a substituent is shown. A plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same as or different from each other. ]

According to such a resin composition, a cured resin having excellent flexibility and impact resistance can be obtained. Moreover, such a resin composition can implement | achieve the moderate viscosity from which workability | operativity, such as a casting operation | work, becomes favorable, and is excellent in molding workability. Furthermore, the cured product of the resin composition of the present invention is excellent in heat resistance, moisture resistance and acid resistance. For this reason, the resin composition is used as a functional sealing material such as a power device sealing material / optical semiconductor sealing material, as a mounting material such as dicing / die bonding, an adhesive application, a casting application, It can use suitably for uses, such as a lamination use.

In the present invention, the epoxy compound is a peak of a peak derived from a heavy mass having a retention time longer than that of the epoxy compound with respect to a peak area A of the peak derived from the epoxy compound in a chromatogram obtained by gas chromatography analysis. It is preferable that the area B is purified so that the ratio B / A is 2.0 × 10 ⁻³ or less. Thereby, the hardened | cured material of a resin composition has sufficient light transmittance with respect to not only visible light but ultraviolet light. Therefore, a resin composition containing such an epoxy compound can be used more suitably in applications such as a sealing material for sealing an optical semiconductor element.

Patent Document 4 describes a thermosetting resin composition used as a substitute for a glass substrate used in a liquid crystal panel or the like. In such a field, light other than visible light (for example, UV) -A (ultraviolet light such as 315 to 400 nm)) is not necessarily required. For this reason, Patent Document 4 does not evaluate light transmittance with respect to light other than visible light, and does not provide any suggestion for obtaining transparency with respect to ultraviolet light. Further, Patent Document 4 describes an example using tetrahydroindene diepoxide, but this example is inferior in light transmittance as compared with other examples.

In the present invention, the epoxy compound is preferably a compound represented by the formula (1-1), more preferably a compound represented by the following formula (1-1-1). According to these epoxy compounds, the effects of the present invention described above are more remarkably exhibited.

The resin composition of the present invention is at least one selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5). A compound may be further blended.

[Wherein, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or a substituent. And Z represents a linking group. The plurality of R ^a , R ^b , R ^c , R ^d , R ^e and R ^f may be the same or different from each other. ]

The present invention also relates to a cured resin product obtained by curing the resin composition. The cured resin of the present invention has excellent flexibility and light transmittance.

The present invention further relates to an optical semiconductor device encapsulated with the above resin composition.

According to the present invention, it is possible to obtain a cured resin having excellent flexibility and impact resistance, and it is possible to realize an appropriate viscosity with good workability such as casting work. A composition is provided. Moreover, according to this invention, the optical semiconductor device sealed using the resin hardened | cured material formed by hardening | curing this resin composition and this resin composition is provided.

2 is a diagram showing a chromatogram obtained by gas chromatography analysis of the component (A-1) obtained in Synthesis Example 1. FIG. FIG. 5 is a diagram showing a chromatogram obtained by gas chromatography analysis of the component (A-5) obtained in Synthesis Example 1.

A preferred embodiment of the present invention will be described below.

The resin composition according to this embodiment is a resin composition formed by blending at least an epoxy compound, an acid anhydride, a curing accelerator, and a polyhydric alcohol. In this embodiment, the epoxy compound is represented by the following formula (1). -1), a compound represented by the following formula (1-2), a compound represented by the following formula (1-3), and a compound represented by the following formula (1-4) More selected epoxy compounds. In the present embodiment, the blending amount of the polyhydric alcohol is 2 to 30 parts by mass with respect to 100 parts by mass of the acid anhydride.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or a substituent. The alkoxy group which may have a group is shown. A plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same as or different from each other.

According to the resin composition according to the present embodiment, a cured resin having excellent flexibility and impact resistance can be obtained. In addition, the resin composition according to the present embodiment can realize an appropriate viscosity that makes workability such as casting work good, and is excellent in moldability. Furthermore, the cured product of the resin composition according to this embodiment is excellent in heat resistance, moisture resistance, and acid resistance. For this reason, the resin composition according to the present embodiment is used as a functional sealing material such as a power device sealing material and an optical semiconductor sealing material, as a mounting material such as dicing and die bonding, an adhesive application, It can be suitably used for applications such as casting and lamination.

Hereinafter, in some cases, the compound represented by the formula (1-1), the compound represented by the formula (1-2), the compound represented by the formula (1-3), and the formula (1-4) An epoxy compound selected from the group consisting of the following compounds is referred to as “component (A)”, an acid anhydride is referred to as “component (B)”, a curing accelerator is referred to as “component (C)”, and a polyhydric alcohol Is referred to as “component (D)”.

<(A) component>
The component (A) is a compound represented by the formula (1-1), a compound represented by the formula (1-2), a compound represented by the formula (1-3), and a compound represented by the formula (1-4). An epoxy compound selected from the group consisting of:

In the chromatogram obtained by gas chromatography analysis, the component (A) is a peak area of a peak derived from a heavy mass having a retention time longer than that of the component (A) with respect to the peak area A of the peak derived from the component (A). It is preferably purified so that the B ratio B / A is 2.0 × 10 ⁻³ or less (more preferably 1.3 × 10 ⁻³ or less).

Thereby, the cured product of the resin composition has sufficient light permeability not only for visible light but also for ultraviolet light. Therefore, the resin composition containing the purified component (A) is more suitable for applications such as a sealing material for sealing an optical semiconductor element.

Patent Document 4 describes a thermosetting resin composition used as a substitute for a glass substrate used in a liquid crystal panel or the like. In such a field, light other than visible light (for example, UV) -A (ultraviolet light such as 315 to 400 nm)) is not necessarily required. For this reason, Patent Document 4 does not evaluate light transmittance with respect to light other than visible light, and does not provide any suggestion for obtaining transparency with respect to ultraviolet light. Further, Patent Document 4 describes an example using tetrahydroindene diepoxide, but this example is inferior in light transmittance as compared with other examples.

When the ratio B / A exceeds 2.0 × 10 ⁻³ , for example, the light transmittance of the resin cured product with respect to light near 800 nm is good, but the light transmittance with respect to UV-A (315 to 400 nm) is extremely low. Become. On the other hand, when the ratio B / A is 2.0 × 10 ⁻³ or less, a cured resin product having sufficient light transmittance not only for visible light but also for ultraviolet light (for example, UV-A) can be obtained. can get.

(A) The component may be a mixture of stereoisomers. When the component (A) is a mixture of stereoisomers, the peak area A indicates the total area of peaks derived from the respective stereoisomers, and “the heavy mass component having a longer retention time than the component (A)” (A) A component having a longer retention time than that having the longest retention time among the stereoisomers of the component.

1 and 2 are diagrams showing chromatograms obtained by gas chromatography analysis of the epoxy compound obtained in Synthesis Example 1 described later. In FIGS. 1 and 2, the peaks indicated by a-1, a-2, a-3 and a-4 are peaks derived from the stereoisomers of the component (A), and peaks in the range indicated by b are shown. It is a peak derived from heavy mass.

Gas chromatography analysis can be performed under the following conditions.
-Equipment used: Agilent Technologies 6850 series-Column: Agilent 19091Z-413E (HP-1 dimethylpolysiloxane, capillary 30.0 m x 320 m x 0.25 m)
Inlet: 250 ° C
・ Detector: 250 ° C
・ Oven: 50 ° C. (10 min), 250 ° C. (5 ° C./min), 250 ° C. (20 min)

Moreover, peak analysis can be performed by gas chromatograph mass spectrometry under the following conditions.
(A) Gas chromatograph unit / equipment: 7890A manufactured by Agilent Technologies
Column: Agilent 19091S-936 (HP-1MS dimethylpolysiloxane, capillary 60.0 m × 250 μm × 0.25 μm)
Inlet: 250 ° C
・ Oven: 40 ° C. (10 min), 300 ° C. (5 ° C./min), 300 ° C. (18 min)
(B) Mass spectrometer / equipment: 5975C VL MSD manufactured by Agilent Technologies
・ Ionization method: Electron impact ionization method ・ Ion source temperature: 230 ° C.
MS quadrupole temperature: 150 ° C

For example, when an epoxy compound of Synthesis Example 1 described later is subjected to gas chromatograph mass spectrometry, peaks corresponding to the peaks indicated by a-1, a-2, a-3 and a-4 in FIGS. 1 and 2 are obtained. A peak derived from a compound having a molecular weight of 152 is observed. From this, it can be confirmed that the peaks indicated by a-1, a-2, a-3 and a-4 are peaks derived from the component (A). In addition, as a peak corresponding to the peak in the range shown in FIG. 1 and FIG.

In the component (A), the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. When the alkyl group has a substituent, examples of the substituent include a halogen atom and an alkoxy group.

In the component (A), the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. When the alkoxy group has a substituent, examples of the substituent include a halogen atom and an alkoxy group.

In the above formula, R ¹ , R ³ , R ⁵ and R ⁷ are preferably a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group, preferably a hydrogen atom or a fluorine atom, and a hydrogen atom. Is more preferable.

R ² , R ⁴ , R ⁶ and R ⁸ are preferably a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group, and may be a hydrogen atom or a fluorine atom, or may be a hydrogen atom. .

As the component (A), a compound represented by the formula (1-1) can be particularly preferably used. In the compound represented by the formula (1-1), the effect of the present invention described above (particularly, the effect obtained by setting the ratio B / A to 2.0 × 10 ⁻³ or less) is more remarkably exhibited.

As the component (A), a compound represented by the formula (1-1-1) is more preferable. In the compound represented by the formula (1-1-1), the effect of the present invention described above (particularly, the effect obtained by setting the ratio B / A to 2.0 × 10 ⁻³ or less) is more remarkably exhibited. The

As an example of a method for producing the component (A), a method for producing a compound represented by the formula (1-1) (hereinafter sometimes referred to as “compound (1-1)”) is shown below.

Compound (1-1) can be produced by a production method comprising the following oxidation step and purification step. In the oxidation step, compound (1-1) is synthesized by an oxidation reaction of the compound represented by the following formula (2).

The method of the oxidation reaction is not particularly limited, and for example, it can be performed by the method described in JP-A No. 2004-182648.

The oxidation reaction can also be performed by a method for producing an epoxy compound from a conventionally known olefin compound. Examples of such a method include J. Org. Org. Chem. 2000, 65, 8651, Organic Synthesis, 1997, 74, 91, Organic Synthesis, Coll. 1998, 9, 288, and the like.

As a specific example of the oxidation reaction, 30% hydrogen peroxide solution was added to a dichloromethane solution containing a compound represented by the formula (2), pyridine, 3-cyanopyridine and methyltrioxorhenium, and room temperature ( 25 ° C.).

In the purification step, in the chromatogram obtained by gas chromatography analysis, the peak derived from the heavy mass component having a retention time longer than that of the compound (1-1) relative to the peak area A ₁ of the peak derived from the compound (1-1) The compound (1-1) obtained in the oxidation step is purified so that the ratio B ₁ / A ₁ of the peak area B ₁ is 2.0 × 10 ⁻³ or less.

The purification method of the compound (1-1) is not particularly limited as long as the ratio B ₁ / A ₁ is 2.0 × 10 ⁻³ or less, and examples thereof include distillation purification.

Since the compound (1-1) is a thermally unstable compound, if the temperature in distillation purification is too high or the residence time is too long, a part of the compound (1-1) is decomposed or heavy mass Minutes may occur. Therefore, in distillation purification, it is preferable to set the temperature to 20 to 150 ° C. and the residence time to 0.01 to 60 minutes. Examples of the distillation apparatus include a batch precision distillation apparatus, a centrifugal molecular distillation apparatus, and a thin film distillation apparatus.

More specifically, the distillation purification is performed, for example, in the range of 600 Pa and the column bottom temperature of 30 to 80 ° C., and the fraction that flows out is fractionated in order, and the ratio B ₁ / A ₁ is 2.0 × 10 ^−3. The following fraction can be taken out.

The chlorine content of the component (A) is preferably 100 ppm or less, more preferably 10 ppm or less, because the moisture resistance reliability of the cured resin is further improved and is more suitable for optical semiconductor sealing applications. . The chlorine content is a value measured according to JIS standard K-7243-3. Specifically, the component (A) is dissolved in diethylene glycol monobutyl ether and heated under reflux with a potassium hydroxide alcohol solution. This is a value measured by saponification and potentiometric titration of a silver nitrate solution.

The chlorine content of the component (A) can be reduced by the above-described distillation purification, and can also be reduced by methods such as alkaline aqueous solution washing and adsorbent treatment.

The metal content of the component (A) is preferably 100 ppm or less, more preferably 10 ppm or less, since the mechanical properties and electrical properties of the cured resin are further improved and become more suitable for optical semiconductor sealing applications. More preferred. The metal content can be measured by inductively coupled plasma emission (ICP emission) analysis of a 10% toluene solution of component (A). As the measuring device, for example, Optima4300DV manufactured by PerkinElmer, Inc. can be used. In this measurement, for the metal species detected by qualitative analysis, quantitative analysis can be performed using a calibration curve created using a commercially available metal standard solution.

The metal content of the component (A) can be reduced by the above-described distillation purification, and can also be reduced by a method such as alkaline aqueous solution washing and adsorbent treatment.

The compounding amount of the component (A) is preferably 12 to 45% by mass, more preferably 14 to 38% by mass based on the total amount of the resin composition.

<(B) component>
(B) A component is an acid anhydride and is a component which reacts with the epoxy compound in a resin composition, and hardens a resin composition. As component (B), phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl end Examples include ethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, and the like.

As the component (B), hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride or a mixture thereof can be particularly preferably used.

The blending amount of the component (B) is an effective amount capable of exhibiting the effect as a curing agent, that is, 1 equivalent of epoxy of the epoxy compound (including the component (A) and the component (A ′) described later) in the resin composition. Is preferably 0.6 to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.

<(C) component>
(C) The hardening accelerator of a component is a component which accelerates | stimulates reaction of the epoxy compound in a resin composition, and (B) component, and accelerates | stimulates the hardening reaction of a resin composition. Examples of the component (C) include tertiary amines, imidazoles, carboxylic acid metal salts, and phosphorus compounds.

Tertiary amines include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3. 0] nonene-5 and the like. Examples of imidazoles include 2-methylimidazole and 2-ethyl-4-methylimidazole.

Examples of the carboxylic acid metal salt include zinc octylate and tin octylate. Examples of the phosphorus compound include tetraphenylphosphonium bromide, tetra-n-butylphosphonium o, o-diethyl phosphorodithioate, and the like.

Component (C) is blended in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy compound (including component (A) and component (A ′) described below) in the resin composition. The amount is preferably 0.2 to 2 parts by mass.

<(D) component>
The blending amount of the polyhydric alcohol (D) is 2 to 30 parts by mass with respect to 100 parts by mass of the acid anhydride. In the present embodiment, the above-described excellent effect is achieved by blending the predetermined amount of the component (D) in combination with the specific component (A), component (B) and component (C) described above. . When the blending amount of the component (D) is too small, the strength of the cured product tends to decrease, and conversely, when it is too large, the heat resistance tends to decrease.

The blending amount of the component (D) is preferably 2 to 30 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the acid anhydride. By blending the component (D) in such a blending amount, the above-described effects are more remarkably exhibited.

The component (D) is preferably a trihydric alcohol or a dihydric alcohol, and more preferably a dihydric alcohol.

Specific examples of the component (D) include ethylene glycol and dehydrated condensates thereof (polyethylene glycol such as diethylene glycol and triethylene glycol), propylene glycol and dehydrated condensates thereof (polyethylene glycol such as dipropylene glycol and tripropylene glycol), Examples include 1,4-butanediol and 1,6-hexanediol.

Polyethylene glycol preferably has a number average molecular weight of 200 to 3,000, more preferably 200 to 2,000. The polypropylene glycol preferably has a number average molecular weight of 200 to 3,000, more preferably 200 to 2,000. If the number average molecular weight is too large, the miscibility between the epoxy compound and the component (D) decreases, the water resistance and solvent resistance decrease, and the toughness and flex resistance decrease locally. There is a case.

The resin composition may contain components other than those described above. For example, the resin composition may further contain an antioxidant (hereinafter sometimes referred to as “component (E)”).

(E) As a component, a phenolic antioxidant, sulfur antioxidant, phosphorus antioxidant, etc. are mentioned.

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and 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-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9- Bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-te Bisphenols such as traoxaspiro [5.5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-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, tocophenol and the like.

Examples of the sulfur antioxidant include dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like.

Phosphorous antioxidants include triphenyl phosphite, tridecyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris (2,4-di -T-butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl Bis (2,4-di-tert-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite Phosphi etc. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa Oxaphosphaphenanthrene oxides such as -10-phosphaphenanthrene-10-oxide; and the like.

The compounding amount of the component (E) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the epoxy compound (including the component (A) and the component (A ′) described later) in the resin composition. The amount is preferably 0.1 to 4 parts by mass.

The resin composition may further contain an epoxy compound other than the component (A) (hereinafter sometimes referred to as “(A ′) component”).

Examples of the (A ′) component include compounds having an alicyclic epoxy group. Examples of the compound having an alicyclic epoxy group include a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5).

In formula (3), R ^a and R ^b each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an optionally substituted alkoxy group, R ^a and R ^b may be the same as or different from each other. R ^a and R ^b are each independently preferably ^a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or a fluorine atom, and even more preferably a hydrogen atom. Examples of the alkyl group and alkoxy group in R ^a and R ^b include the same groups as the alkyl group and alkoxy group in R ¹ to R ¹² .

In Formula (4), R ^c and R ^d each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an optionally substituted alkoxy group, R ^c and R ^d may be the same or different from each other. R ^c and R ^d are each independently preferably a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or a fluorine atom, and even more preferably a hydrogen atom. Examples of the alkyl group and alkoxy group in R ^c and R ^d include the same groups as the alkyl group and alkoxy group in R ¹ to R ¹² .

In formula (5), R ^e and R ^f each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an optionally substituted alkoxy group, and Z represents A linking group is shown. The plurality of R ^e and R ^f may be the same as or different from each other. R ^e and R ^f are each independently preferably a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or a fluorine atom, and even more preferably a hydrogen atom. Examples of the alkyl group and alkoxy group in R ^e and R ^f include the same groups as the alkyl group and alkoxy group in R ¹ to R ¹² .

Examples of the linking group include a single bond, a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), carbonate, and the like. A bond (—OCOO—) and a group in which a plurality of these are linked.

The carbon number of the divalent hydrocarbon group is preferably 1-18. Moreover, as said bivalent hydrocarbon group, a linear or branched alkylene group, a bivalent alicyclic hydrocarbon group (especially cycloalkylene group), etc. are preferable. Examples of the alkylene group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Divalent alicyclic hydrocarbon groups include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. Examples include a silene group, 1,4-cyclohexylene group, cyclohexylidene group and the like.

Specific examples of the compound represented by the formula (5) include compounds represented by the following formulas (5-1) to (5-7).

Examples of the compound having an alicyclic epoxy group include dicyclopentadiene dioxide, limonene dioxide, di (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexane. Carboxylate (commercially available products include Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.)), (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene-1, Examples thereof include 2-di (3,4-epoxycyclohexanecarboxylic acid) ester.

As the compound having an alicyclic epoxy group, among the above, the compound represented by the formula (3), the compound represented by the formula (4), the compound represented by the formula (5) (particularly 3, 4 -Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexylmethyl alcohol and 3,4-epoxycyclohexylethyltrimethoxysilane can be preferably used.

Further, as the component (A ′), a compound having an epoxy group other than the alicyclic epoxy group can also be used. Examples of such compounds include diglycidyl ethers of various bisphenol types typified by bisphenol A type and bisphenol F type (as commercially available products, Epicoat 828,806 (manufactured by Japan Epoxy Resin), YD-128 (manufactured by Tohto Kasei) )); Nuclear hydrogenated products of bisphenol type epoxy resins (commercially available products such as HBE-100 (manufactured by Nippon Nippon Chemical Co., Ltd.), YX-4000, YX-8000 (manufactured by Japan Epoxy Resin Co., Ltd.)); cyclohexanedimethanol Glycidyl ethers with a cyclic aliphatic skeleton such as diglycidyl ether (commercially available products such as DME-100 (manufactured by Shin Nippon Chemical Co., Ltd.)); glycidyl ether of novolac type phenol resin; DCPD (dicyclopentadiene), etc. Of novolac phenolic resin Ether: Polycyclic aromatic glycidyl ether such as naphthalene; Epoxy resin having terminal epoxy in alicyclic skeleton (commercially available products are EHPE-3150, EHPE-3150CE (manufactured by Daicel Chemical Industries), etc.); Silicone resins (commercially available products such as A-186 (manufactured by Nihon Unicar), KBM303, KBM403, KBM42 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.);

(A ') component can be used individually by 1 type or in combination of 2 or more types.

When the component (A ′) is blended, the ratio A ′ / A (mass ratio) of the blending amount A ′ of the component (A ′) to the blending amount A of the component (A) is 1/99 to 99/1. 1/99 to 90/10.

Furthermore, additives such as ultraviolet absorbers may be further blended in the resin composition as components other than those described above.

The viscosity of the resin composition is preferably 30 to 300 mPa · s, more preferably 80 to 200 mPa · s, from the viewpoint of good moldability. The resin composition according to the present embodiment employs the specific components (A) to (D), so that the viscosity range can be easily achieved. For example, in this embodiment, the viscosity of the resin composition can be reduced by increasing the proportion of the component (A) in the entire epoxy compound in the resin composition.

The resin composition according to this embodiment is cured by heating to form a cured resin. The cured resin thus formed is not only light transmissive to visible light but also sufficiently light transmissive to light other than visible light (for example, UV-A (315 to 400 nm) or other ultraviolet light). Have Therefore, the resin composition according to the present embodiment can be suitably used for applications that require light transmittance of a cured product, such as a sealing material for sealing an optical semiconductor element.

In addition, an optical semiconductor device can be obtained by injecting the resin composition according to the present embodiment into a predetermined mold, and heat curing under predetermined conditions to seal the optical semiconductor element. Since such an optical semiconductor device protects the periphery of the light emitter by using the resin composition according to the present embodiment as a sealing material, there is no problem of luminance reduction or discoloration due to yellowing, and a highly reliable optical semiconductor. Useful as a device.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

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

(Synthesis Example 1)
A reaction vessel equipped with a stirrer was charged with 120 g of tetrahydroindene, 15.8 g of pyridine, 20.8 g of 3-cyanopyridine, 2.49 g of methyltrioxorhenium, 440 g of dichloromethane, and 450 g of 30% hydrogen peroxide solution in this order. After stirring at room temperature for 2 hours, the oil phase and the aqueous phase were separated. To the aqueous phase, 200 g of dichloromethane was added and stirred to wash the aqueous phase. The oil phase produced by the washing operation was mixed with the previous oil phase, and the solvent was distilled off using a rotary evaporator to obtain a crude product.

The obtained crude product was distilled under the conditions of 0 ° C. and 220 Pa to obtain 143 g of an epoxy compound represented by the formula (1-1-1). When the obtained epoxy compound was subjected to gas chromatography analysis, the ratio of the peak area B of the peak derived from the heavy mass having a longer retention time than the epoxy compound to the peak area A of the peak derived from the epoxy compound B / A was 5.7 × 10 ⁻³ . This epoxy compound was used as component (A-5).

Next, 100 g of component (A-5) was charged into a precision distiller, and subjected to precision distillation at 600 Pa and a tower bottom temperature of 30 to 80 ° C., and the fraction that flowed out was fractionated in order. Gas chromatographic analysis was performed on the four fractions, and the ratio B / A was 1.0 × 10 ⁻³ , 1.1 × 10 ⁻³ , 1.6 × 10 ⁻³ , and 3. It was 0 × 10 ⁻³ . These four fractions were designated as component (A-1), component (A-2), component (A-3), and component (A-4), respectively. With respect to 100 g of component (A-5), the distillation yield of component (A-1) is 20 g, the distillation yield of component (A-2) is 20 g, the distillation yield of component (A-3) is 20 g, (A- 4) The distillation yield of the component was 35 g. These results are shown in Table 1.

Gas chromatography analysis was performed under the following conditions.
-Equipment used: Agilent Technologies 6850 series-Column: Agilent 19091Z-413E (HP-1 dimethylpolysiloxane, capillary 30.0 m x 320 m x 0.25 m)
Inlet: 250 ° C
・ Detector: 250 ° C
・ Oven: 50 ° C. (10 min), 250 ° C. (5 ° C./min), 250 ° C. (20 min)

FIG. 1 is a diagram showing a chromatogram obtained by gas chromatography analysis of the component (A-1), and FIG. 2 is a chromatogram obtained by gas chromatography analysis of the component (A-5). FIG.

The light transmittance (%) at wavelengths of 350 nm, 400 nm, and 800 nm of the components (A-1) to (A-5) was measured with a spectrophotometer (manufactured by JASCO: V-570). The measurement results were as shown in Table 2.

(Examples 1 to 10, Comparative Examples 1 to 3)
Each raw material was blended in the number of parts (parts by mass) shown in Table 3, Table 4 or Table 5, and stirred at room temperature to obtain a liquid resin composition. As the component (A ′), Celoxide 2021P (manufactured by Daicel Chemical Industries, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate) was used. As the component (B) of the acid anhydride, a 7: 3 (molar ratio) mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was used. As the component (C) of the curing accelerator, Hishicolin PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd., tetra-n-butylphosphonium o, o-diethyl phosphorodithioate) was used. Moreover, polypropylene glycol (number average molecular weight 400) was used as the (D) component of the polyhydric alcohol. Antioxidants include 2,6-di-t-butyl-p-cresol (referred to as “(E-1) component” in Tables 3 to 5) and triphenyl phosphite (Tables 3 to 5). Among them, it is expressed as “(E-2) component” ”. ) Was used.

The resin compositions obtained in Examples and Comparative Examples were evaluated by the following methods. The evaluation results are as shown in Table 6, Table 7 and Table 8.

(1) Measurement of viscosity (according to JIS K7117-2)
Device: TVE-22LT (manufactured by Toki Sangyo)
Test temperature: 23 ° C
Cone rotor: 1 ° 23 '× R24
Sample: 1.1 mL of component (A-1), component (A ′), component (B), component (D) among components shown in Examples and Comparative Examples
Rotation speed: 0.5-50rpm
Incubation time: 5 minutes Measurement time: 2 minutes

(2) Preparation of cured product 60-70 g of the resin composition was vacuum degassed at 3-5 mmHg × 2 minutes, then poured into a 210 mm × 100 mm × 3 mm mold, heated at 100 ° C. × 2 hours and 120 ° C. × It hardened | cured by the heating for 2 hours and 150 degreeC x 10 hours, and the test piece which consists of resin cured | curing material was obtained. Using this test piece, the following (2-1), (2-2) and (2-3) were evaluated.

(2-1) Bending test evaluation of cured products (conforming to JIS K6911)
Equipment: 5582 type universal material testing machine (Instron)
Test piece: 70 mm x 25 mm x 3 mm
Test temperature: 23 ° C
Test speed: 1.5mm / min
Distance between fulcrums: 48mm

(2-2) Impact test evaluation of cured products (conforming to JIS K6911)
Equipment: DG-UB type digital impact tester (manufactured by Toyo Seiki Seisakusho)
Test piece: 63.5 mm x 12.7 mm x 3 mm
Test temperature: 23 ° C
Notch: Type A, r _N = 0.25, remaining width 10.2 mm
Hammer weighing: 0.5J

(2-3) Light transmittance test evaluation of cured product Apparatus: UV-visible spectrophotometer V-630 (manufactured by JASCO)
Test piece: 30 to 40 mm x 40 mm x 3 mm
Wavelength: 400nm

Claims (7)

1. A resin composition comprising at least an epoxy compound, an acid anhydride, a curing accelerator and a polyhydric alcohol,
   The epoxy compound is a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), a compound represented by the following formula (1-3), and the following formula (1-4). Is an epoxy compound selected from the group consisting of compounds represented by:
   The resin composition, wherein the amount of the polyhydric alcohol is 2 to 30 parts by mass with respect to 100 parts by mass of the acid anhydride.
   

   

   

   

   

   [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or The alkoxy group which may have a substituent is shown. A plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same as or different from each other. ]
2. In a chromatogram obtained by gas chromatography analysis of the epoxy compound, a ratio of a peak area B of a peak derived from a heavy mass having a retention time longer than that of the epoxy compound to a peak area A of a peak derived from the epoxy compound The resin composition according to claim 1, wherein the resin composition is purified so that B / A is 2.0 × 10 ⁻³ or less.
3. The resin composition according to claim 1 or 2, wherein the epoxy compound is a compound represented by the formula (1-1).
4. 4. The resin composition according to claim 3, wherein the epoxy compound is a compound represented by the following formula (1-1-1).
   

   
5. A compound represented by the following formula (3), a compound represented by the following formula (4), and at least one compound selected from the group consisting of the compound represented by the following formula (5); The resin composition according to any one of claims 1 to 4.
   

   

   

   

   [Wherein, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or a substituent. And Z represents a linking group. The plurality of R ^a , R ^b , R ^c , R ^d , R ^e and R ^f may be the same or different from each other. ]
6. A cured resin obtained by curing the resin composition according to any one of claims 1 to 5.
7. An optical semiconductor device sealed with the resin composition according to any one of claims 1 to 5.

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