JP6143515B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition and an optical semiconductor sealing material comprising the same.

Various types of optical semiconductor devices (semiconductor light-emitting devices) each having a pn junction formed of a semiconductor layer grown on a crystal substrate and an LED (light-emitting diode) chip having the junction region as a light-emitting layer as a light-emitting element Widely used in display devices, display devices, and the like.
Examples of this optical semiconductor device include visible light emitting devices and high temperature operating electronic devices using gallium nitride compound semiconductors such as GaN, GaAlN, InGaN and InAlGaN. Recently, blue light emitting diodes and ultraviolet light emitting diodes are used. Development is progressing in this field.

An optical semiconductor device including an LED chip as a light emitting element includes an LED chip mounted on a light emitting surface side of a lead frame, and electrically connecting the LED chip and the lead frame by wire bonding. It is sealed with a resin that also functions as a lens. A sealing material used when sealing a light emitting element such as an LED chip is required to have transparency, heat resistance, and light resistance.
As an example of such a sealing material, for example, Patent Document 1 discloses a polymer obtained by homopolymerizing or copolymerizing an alicyclic acrylic acid ester or methacrylic acid ester having 10 or more carbon atoms.
Patent Documents 2 and 3 disclose materials using a composition containing a (meth) acrylate compound in which an alicyclic hydrocarbon group having 6 or more carbon atoms is ester-bonded.

However, phosphors and light diffusing agents that are added to improve the optical characteristics of the LED encapsulant tend to settle and not uniformly disperse in the raw material composition. While it requires a high viscosity, if the viscosity is too high, it is difficult to handle and is not suitable for mass production.
Therefore, there is a need for a sealing material having excellent heat resistance and light resistance, having a long life, and a composition having an appropriate viscosity capable of providing such a sealing material.

JP-A-2-67248 International Publication No. 2007/129536 Pamphlet International Publication No. 2011/016356 Pamphlet

  The objective of this invention is providing the composition which has the moderate viscosity which can provide the sealing material of the optical semiconductor device which was excellent in mass productivity with long life, and such a sealing material.

（式中、Ｒ^１及びＲ^３は水素原子又はメチル基であり、Ｒ^２は環状脂肪族基である。）
２．脂肪族エポキシ化合物を２０質量％以下含む１に記載の樹脂組成物。
３．Ｒ^２が置換もしくは無置換のアダマンチル基、置換もしくは無置換のジシクロペンタニル基、又は置換もしくは無置換のイソボルニル基である１又は２に記載の樹脂組成物。
４．硬化促進剤を含む１〜３のいずれかに記載の樹脂組成物。
５．前記共重合体中に含まれる繰り返し単位（Ａ）に対応する単量体及び繰り返し単位（Ｂ）に対応する単量体の合計が５重量％以下である１〜４のいずれかに記載の樹脂組成物。
６．前記共重合体中に含まれる全塩素量が１．１０重量％以下である１〜５のいずれかに記載の樹脂組成物。
７．１〜６のいずれかに記載の樹脂組成物からなる光半導体封止材。 According to the present invention, the following resin composition and the like are provided.
1. Copolymer having a proportion of the repeating unit (A) represented by the following formula (I) of 40 to 80 mol% and a proportion of the repeating unit (B) represented by the following formula (II) of 20 to 60 mol% A resin composition comprising 5 to 40% by mass of a coal, 5 to 20% by mass of triglycidyl isocyanurates and 40 to 60% by mass of an acid anhydride.

(In the formula, R ¹ and R ³ are a hydrogen atom or a methyl group, and R ² is a cyclic aliphatic group.)
2. 2. The resin composition according to 1, which contains 20% by mass or less of an aliphatic epoxy compound.
3. ^3. The resin composition according to 1 or 2, wherein R ² is a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dicyclopentanyl group, or a substituted or unsubstituted isobornyl group.
4). The resin composition in any one of 1-3 containing a hardening accelerator.
5). Resin in any one of 1-4 whose sum total of the monomer corresponding to the repeating unit (A) contained in the said copolymer and the monomer corresponding to a repeating unit (B) is 5 weight% or less. Composition.
6). The resin composition according to any one of 1 to 5, wherein the total amount of chlorine contained in the copolymer is 1.10% by weight or less.
7.1 An optical semiconductor sealing material comprising the resin composition according to any one of 1 to 6.

  ADVANTAGE OF THE INVENTION According to this invention, the composition which has the moderate viscosity which can provide the sealing material of the optical semiconductor device which was excellent in mass productivity with a long lifetime can be provided.

（式中、Ｒ^１及びＲ^３は水素原子又はメチル基であり、Ｒ^２は環状脂肪族基である。） In the resin composition of the present invention, the proportion of the repeating unit (A) represented by the following formula (I) is 40 to 80 mol%, and the proportion of the repeating unit (B) represented by the following formula (II) is 20 It contains 5 to 40% by mass of a copolymer of ˜60 mol%, 5 to 20% by mass of triglycidyl isocyanurates, and 40 to 60% by mass of an acid anhydride.

(In the formula, R ¹ and R ³ are a hydrogen atom or a methyl group, and R ² is a cyclic aliphatic group.)

In the above copolymer, the cycloaliphatic group of R ² is preferably an adamantyl group or a substituted adamantyl group, a dicyclopentanyl group or a substituted dicyclopentanyl group, or an isobornyl group or a substituted isobornyl group.
“Substituted adamantyl group” means a group in which a hydrogen atom of an adamantyl group is substituted with a substituent such as a hydroxyl group. The same applies to “substituted dicyclopentanyl group” and “substituted isobornyl group”.
Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hydroxyl group, carboxyl group and halogen.

  By containing the repeating unit (A), the above copolymer can give a cured product excellent in light resistance and heat resistance. Moreover, the hardened | cured material excellent in hardness can be given by including a repeating unit (B).

Said copolymer contains 40-80 mol% of repeating units (A) and 20-60 mol% of repeating units (B) with respect to the total of repeating units (A) and (B).
When the molar ratio of the repeating unit (A) is less than 40 mol%, the obtained cured product may be inferior in heat resistance, and when it exceeds 80 mol%, it is a phase with other components when the composition is formed. Solubility may deteriorate. Preferably, the proportion of the repeating unit (A) is 45 to 75 mol%, and the proportion of the repeating unit (B) is 25 to 55 mol%.
The molar ratio of the repeating units (A) and (B) can be measured by ¹ H-NMR, and specifically can be measured by the method described in the examples.

  The blending amount of the copolymer is 5 to 40% by mass, preferably 10 to 40% by mass, and more preferably 15 to 40% by mass with respect to the resin composition.

The weight average molecular weight of the copolymer is preferably 4,000 to 15,000, more preferably 4000 to 10,000. Such a range is preferable because it is excellent in solubility in a solvent, compatibility with a curing agent such as an acid anhydride, and compatibility with other epoxy resins.
In addition, a weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

（式中、Ｒ^１〜Ｒ^３は上記と同じである。） The total of the monomer (monomer) corresponding to the repeating unit (A) and the monomer corresponding to the repeating unit (B) contained in the copolymer is preferably 5% by weight or less.
The monomer corresponding to the repeating unit (A) is a monomer (A ′) represented by the following formula (I ′), and the monomer corresponding to the repeating unit (B) is represented by the following formula (II ′): It is a monomer (B ') represented by these.

(Wherein R ^{1 to} R ³ are the same as above)

When the total of the monomers (A ′) and (B ′) (for example, raw material monomers remaining without being polymerized) contained in the copolymer is 5% by weight or less, the heat resistance of the resulting cured product is reduced. improves.
The total of the monomers (A ′) and (B ′) contained in the copolymer is preferably 4% by weight or less, more preferably 3% by weight or less.
The contents of the monomers (A ′) and (B ′) can be measured by gel permeation chromatography (GPC), and specifically can be measured by the method described in the examples.

Moreover, it is preferable that the total amount of chlorine contained in the copolymer is 1.10% by weight or less. When the total chlorine amount is 1.10% by weight or less, the heat resistance of the obtained cured product is improved.
The total amount of chlorine contained in the copolymer is preferably 1.00% by weight or less, more preferably 0.86% by weight or less.

  The total amount of chlorine contained in the copolymer can be measured by a combustion-ion chromatography method, and specifically, can be measured by the method described in the examples.

  The above copolymer is a copolymer of 40 to 80 mol% of the monomer (A ′) represented by the formula (I ′) and 20 to 60 mol% of the monomer (B ′) represented by the formula (II ′). Can be manufactured.

The monomer (A ′) can be radically polymerized with a (meth) acrylate monomer (B ′) having an epoxy group by a (meth) acryl group exhibiting radical polymerizability. A copolymer having an epoxy group that is cationically polymerizable and a cyclic aliphatic structure such as adamantane can be provided.
A cured product can be provided by reaction of a cationically polymerizable functional group in the copolymer, that is, an epoxy group.

  The copolymerization reaction of the monomer (A ′) and the monomer (B ′) is usually performed by radical polymerization. As the radical polymerization initiator, an azo initiator, a peroxide initiator, or the like can be used.

  Examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1'-azobis-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropene) dihydrochloride Salt, 2-tert-butylazo-2-cyanopropane, 2,2′-azobis- (2-methyl-propionamide) dihydrate, 2,2′-azobis [2- (2-imidazolin-2-yl ) Propene], 2,2′-azobis (2,2,4-trimethylpentane) and the like.

  Examples of the peroxide initiator include ketone peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1, 1, 3, 3 -Hydroperoxides such as tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxides such as oxide and m-toluylbenzoyl peroxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Dialkyl peroxides such as hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butyl) Peroxyketals such as peroxy) butane; (4-t-butylcyclohexyl) peroxydicarbonate and the like.

The usage-amount of a radical polymerization initiator is 0.01-50 mass parts normally with respect to a total of 100 mass parts of a monomer (A '), a monomer (B'), and a radical polymerization initiator, Preferably it is 0.8. 01 to 30 parts by mass.
By setting it as the said range, reaction time, a yield, etc. become favorable, the target weight average molecular weight is obtained, and also physical properties, such as an optical characteristic, can be expressed.

  The copolymerization reaction of the monomer (A ′) and the monomer (B ′) may be solventless, but a solvent can be used as necessary. The solvent is used in such an amount that the total concentration of the monomers (A ′) and (B ′) is usually 0.5% by mass or more, preferably 5% by mass or more. At this time, the monomer may be in a suspended state but is preferably dissolved.

  Examples of the solvent include alkyl alcohols such as methanol, ethanol, n-propanol, and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; benzene , Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Mixed hydrocarbons containing aromatic hydrocarbons such as 2 (manufactured by Exxon USA); aliphatic hydrocarbons such as n-pentane and n-hexane; Isopar C, Isopar E, Exol DSP 100/140, Exol D30 ( Mixed hydrocarbons containing aliphatic hydrocarbons such as Exxon, USA) and IP Solvent 1016 (produced by Idemitsu Kosan Co., Ltd.); alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; tetrahydrofuran, dioxane , Ethers such as diisopropyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-amyl, isoamyl acetate, hexyl acetate, ethyl propionate , Propylene glycol mono Esters such as chill ether acetate and the like. These solvents can be used alone or in combination.

The reaction temperature is usually 0 to 200 ° C, preferably 20 to 150 ° C. If the temperature is too low, the reaction rate may decrease, and if the temperature is too high, coloring may become intense.
The reaction pressure is usually 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. If the pressure is too high, there is a safety problem and a special device is required, which is not preferable.

The reaction time depends on the type and amount of the polymerization initiator, the reaction temperature, and the like, and cannot be generally determined, but is usually 1 minute to 24 hours, and preferably 1 to 10 hours.
In the reaction, a chain transfer agent can be used as necessary. The chain transfer agent is used for controlling the molecular weight, and examples thereof include dodecyl mercaptan, lauryl mercaptan, thioglycolic acid ester, mercaptoethanol, and α-methylstyrene dimer.

  Moreover, it is preferable to perform the copolymerization reaction by a dropping operation because the amount of unreacted monomer can be reduced. The dropping may be carried out in any way, for example, one of the monomers (A ′) and (B ′) may be dropped into the other solution heated to the reaction temperature, or the monomer (A The solution of ') and (B') may be dropped into the solvent heated to the reaction temperature. The dropping time is usually 1 to 5 hours.

  Furthermore, a method of adding an initiator after the polymerization reaction has progressed is also useful as a method of reducing the amount of unreacted monomers. “After the polymerization reaction has progressed” means, for example, after 80%, preferably 90% of the reaction time has elapsed.

  Examples of the triglycidyl isocyanurates used in the present invention include 1,3,5-triglycidyl isocyanurate (for example, TEPIC-S, TEPIC-SS manufactured by Nissan Chemical Co., Ltd.), a modified product of 1,3,5-triglycidyl isocyanurate. (For example, Nissan Chemical's TEPIC-PAS, TEPIC-VL), 1-methyl-3,5-diglycidyl isocyanurate (for example, Shikoku Kasei MeDGIC), etc. are mentioned.

  The compounding quantity of triglycidyl isocyanurate is 5-20 mass% with respect to a resin composition, Preferably it is 7-20 mass%, More preferably, it is 10-20 mass%.

  Examples of the acid anhydride used in the present invention include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, anhydrous Examples include glutaric acid, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

  The compounding quantity of an acid anhydride is 40-60 mass% with respect to a resin composition, Preferably it is 45-60 mass%, More preferably, it is 45-55 mass%.

Moreover, it is preferable to mix | blend a hardening accelerator in order to accelerate | stimulate hardening.
Examples of the curing accelerator include tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, and tris (2,4,6-dimethylaminomethyl) phenol; 2-ethyl Imidazoles such as -4-methylimidazole and 2-methylimidazole; phosphorus such as triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate Compounds: quaternary ammonium salts, organometallic salts, and derivatives thereof. These curing accelerators may be used alone or in combination.

  The blending of the curing accelerator is usually 0.01 to 8.0 parts by mass, preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the resin composition. By making the content rate of a hardening accelerator into the said range, sufficient hardening acceleration effect is acquired and discoloration is not seen by the hardened | cured material obtained.

The resin composition of this invention should just contain said copolymer, a triglycidyl isocyanurate, and an acid anhydride, may consist of these components substantially, and may consist only of these components.
“Substantially” means that the content of these components in the composition is, for example, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or It means 99 mass% or more.

Moreover, you may mix | blend an aliphatic epoxy compound with the resin composition of this invention for optimization, such as mechanical strength, solubility, and workability | operativity.
Examples of the aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, etc. It is done.
The compounding quantity of an aliphatic epoxy compound is 0-20 mass% normally with respect to a resin composition, Preferably it is 0-15 mass%.

  In addition, the resin composition of the present invention has been conventionally used, for example, known additives such as deterioration inhibitors, modifiers, defoamers, inorganic powders, solvents, leveling agents, mold release agents, dyes, pigments and the like. May be appropriately blended.

  Examples of the deterioration preventing agent include known deterioration preventing agents such as a phenol compound, an amine compound, an organic sulfur compound, and a phosphorus compound. When a deterioration inhibitor is added, it is possible to maintain characteristics such as heat resistance and transparency of the cured product.

Examples of phenolic compounds include Irganox 1010 (Irganox 1010, trade name, manufactured by Ciba Specialty Chemicals), Irganox 1076 (Irganox 1076, trade name, manufactured by Ciba Specialty Chemicals), Irganox 1330 (Irganox 1330, manufactured by Ciba Specialty Chemicals) ), Irganox 3114 (Irganox 3114, Ciba Specialty Chemicals, Trademark), Irganox 3125 (Irganox 3125, Ciba Specialty Chemicals, Trademark), Irganox 3790 (Irganox 3790, Ciba Specialty Chemicals, Trademark) ), BHT, Cyanox 1790 (Cyanox 1790, Cyanamid Co., Ltd.) GA-80 (SumilizerGA-80, manufactured by Sumitomo Chemical Co., Ltd., trademark) can be exemplified commercially available products such as.

  Examples of amine compounds include irgastab FS042 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), GENOX EP (trade name, compound name; dialkyl-N-methylamine oxide), etc. manufactured by Cropton Co., Ltd. ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA-94, Tinuvin123 manufactured by CSC 144, 440, 662, Chimassorb 2020, 119, 944, Hostavin N30 manufactured by Hoechst, Cyasorb UV-3346, UV-3526 manufactured by Cytec, Uval299 manufactured by GLC, and Sanduvor PR-31 manufactured by Clariant, etc. It can gel.

  Examples of the organic sulfur compounds include DSTP (Yoshitomi, trademark), DLTP (Yoshitomi, trademark), DLTOIB (Yoshitomi, trademark), and DMTP (Yoshitomi, trademark). ), Seenox 412S (trade name, manufactured by Sipro Kasei Co., Ltd.) and Cyanox 1212 (trade name, manufactured by Cyanamid Co., Ltd.).

  Examples of the modifier include known modifiers such as glycols, silicones, and alcohols. Examples of the silane coupling agent include known silane coupling agents such as silane and titanate. Examples of the defoaming agent include known defoaming agents such as silicone. As the inorganic powder, those having a particle size of several nanometers to 10 μm can be used depending on applications, and examples thereof include known inorganic powders such as glass powder, silica powder, titania, zinc oxide, and alumina. Solvents can be used when the resin component is powder, or as coating solvents, aromatic solvents such as toluene and xylene, and ketone solvents such as MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), and cyclohexanone. It is.

  By mixing the resin composition of the present invention with other resins or various additives that are blended as necessary, and forming the resin into a desired shape by molding (resin mold) or by coating, and then curing. It can be a cured product.

Although there is no restriction | limiting in particular as a hardening method, Usually, the hardening method by a heat-curing method is mentioned.
As the heat curing method, the curing temperature is usually about 50 to 200 ° C, preferably 100 to 180 ° C. Setting it to 50 ° C. or higher does not cause poor curing, and setting it to 200 ° C. or lower eliminates coloring and the like.
The curing time varies depending on the epoxy resin, the curing agent, the accelerator and the initiator used, but usually 0.5 to 6 hours are preferable.

  The molding method is not particularly limited, such as injection molding, blow molding, press molding and the like.

  Cured products obtained by curing the resin composition of the present invention include optical semiconductors (LEDs, etc.) and optical resins (sealing agents, adhesives, sealing agents), flat panel displays (organic EL elements, etc.). It can be suitably used for optical electronic members such as optical waveguides, optical communication lenses and optical films, resist materials, and the like.

  The structure as a sealant for optical semiconductors (LEDs, etc.) can be applied to the element such as a cannonball type or surface mount (SMT) type, and is in good contact with a semiconductor such as GaN formed on metal or polyamide, It can also be used by dispersing a fluorescent dye such as YAG. Furthermore, it can be used for a surface coating agent for a bullet type LED, a lens for an SMT type LED, and the like.

Examples of copolymer production and examples of the resin composition of the present invention are shown below.
The content of (meth) acrylate contained in the obtained copolymer, the total amount of chlorine contained in the copolymer, and the molar ratio of each repeating unit of the copolymer were measured as follows.

<Content of (meth) acrylate in copolymer>
A calibration curve of each (meth) acrylate was prepared by gel permeation chromatography (manufactured by Tosoh Corporation: HLC-8220GPC), and the calculation was performed from the peak area of each (meth) acrylate detected from the IR detector.
(GPC measurement conditions)
Column: TSKgel G-4000HXL + G-2000HXL
Temperature: 40 ° C
Eluent: Tetrahydrofuran flow rate: 1 ml / min
Detector: RI

<Measurement of total chlorine content in copolymer>
It was measured by combustion-ion chromatography. The automatic sample combustion apparatus used was AQF-100 manufactured by Mitsubishi Chemical Analytech, and the ion chromatograph used DX-120 manufactured by DIONEX.

<Molar ratio of repeating units>
^It was measured by ¹ H-NMR (JNM-ECA500 manufactured by JEOL Ltd.). The measurement conditions for ¹ H-NMR are as follows.
⁽¹ H-NMR measurement conditions)
Solvent: Deuterated chloroform solid concentration: 10 wt%
Internal standard: Tetramethylsilane Temperature: Room temperature

[Production of copolymer]
Production Example 1
In a 500 mL round bottom flask equipped with a reflux condenser, a stirrer, a thermometer, a dropping funnel, and a nitrogen introduction tube, 98.7 g of toluene was placed, and nitrogen bubbling was performed for 30 minutes to raise the temperature to 100 ° C. A solution prepared by dissolving 80.0 g of 1-adamantyl methacrylate, 51.6 g of glycidyl methacrylate, and 6.0 g of azobisisobutyronitrile in 98.7 g of toluene was dropped from the dropping funnel over 2 hours to initiate the polymerization reaction. It was. After completion of the dropwise addition, the reaction was completed for 5 hours to complete the polymerization reaction.
Then, reprecipitation was performed in heptane to obtain a copolymer 1 (m / n = 49/51, Mw: 5,000, epoxy equivalent 375) of 1-adamantyl methacrylate / glycidyl methacrylate represented by the following formula.
The total content of 1-adamantyl methacrylate and glycidyl methacrylate in the obtained copolymer was 1.3 wt%. Further, the total chlorine content in the copolymer was 0.18 wt%.

Production Example 2
In Production Example 1, except that 80.0 g of 1-adamantyl methacrylate was changed to 80.0 g of dicyclopentanyl methacrylate, acrylic resin B (m / n = 50/50, Mw 5,300, epoxy equivalent 372). The total content of dicyclopentanyl methacrylate and glycidyl methacrylate in the obtained copolymer was 1.2 wt%. The total chlorine content in the copolymer was 0.15 wt%.

Production Example 3
A 1000 mL round bottom flask equipped with a reflux condenser, a stirrer, a thermometer, a dropping funnel, and a nitrogen inlet tube was charged with 98.3 g of methyl isobutyl ketone and heated to 100 ° C. by bubbling nitrogen for 30 minutes. A solution prepared by dissolving 80.0 g of isobornyl methacrylate, 51.2 g of glycidyl methacrylate, and 5.9 g of azobisisobutyronitrile in 98.3 g of methyl isobutyl ketone was dropped from the dropping funnel over 2 hours to initiate the polymerization reaction. I let you. After completion of the dropwise addition, the reaction was completed for 5 hours to complete the polymerization reaction.
Then, it was reprecipitated in heptane to obtain a copolymer C (m / n = 49/51, Mw: 5,800, epoxy equivalent 378) of isobornyl methacrylate / glycidyl methacrylate represented by the following formula. The total content of isobornyl methacrylate and glycidyl methacrylate was 1.4 wt%. Further, the total chlorine content in the copolymer was 0.14 wt%.

[Preparation of encapsulating resin composition for optical semiconductors]
Example 1
As the copolymer A 12.0 g obtained in Production Example 1, triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name: “TEPIC-S”, epoxy equivalent 100), 6.0 g, and an acid anhydride 15.2 g of a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: “Licacid MH-700G”) was heated and stirred uniformly at 80 ° C. To this was added 0.2 g of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator, and a liquid resin composition was obtained at 25 ° C. Moreover, no precipitation of components was observed.

[LED conduction test]
A circuit is formed on a PCB substrate, and a package (reflector: made of ceramic) in which a blue LED light emitting element (part number: B2424-DCI0, wavelength 450 to 460 nm, 0.61 mm × 0.61 mm, manufactured by Genelite) is bonded is mounted. The above resin composition was applied onto an LED light emitting device, and was cured by heating and curing at 110 ° C. for 3 hours and at 150 ° C. for 2 hours to obtain a test substrate.

0.15A from a constant current power supply (product number: AD-8724, manufactured by A & D) while placing the test substrate in an oven (product number: SPHH-101, manufactured by Espec) in an atmosphere of 60 ° C. Was turned on continuously.
The amount of luminous flux of the blue LED after the test was measured by a total luminous flux measuring device (product number: MCPD-3700, manufactured by Otsuka Electronics Co., Ltd.), and the decrease in luminous flux was measured. The time until the amount of light flux decreased by 30% from the start of energization was measured, and the case of 168 hours or more was evaluated as ◯ (good) and the case of less than 168 hours was evaluated as x (defective).
The evaluation results are shown in Table 1.

Example 2
6.0 g of copolymer A obtained in Production Example 1, 4.0 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name: “TEPIC-S”, epoxy equivalent 100), 3 as aliphatic epoxy , 4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (manufactured by Daicel Corporation, trade name: “Celoxide 2021P”, epoxy equivalent 130) 4.0 g, and hexahydrophthalic anhydride as the acid anhydride And 14.3 g of a mixture of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: “Licacid MH-700G”) was heated and stirred at 80 ° C. to make it uniform. To this was added 0.1 g of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator to obtain a uniform resin composition at 25 ° C. Moreover, no precipitation of components was observed. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
In Example 2, a liquid resin composition was obtained at 25 ° C. in the same manner as in Example 2 except that the copolymer A was changed to the copolymer B obtained in Production Example 2. No component precipitation or the like was observed. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
In Example 2, a liquid resin composition was obtained at 25 ° C. in the same manner as in Example 2 except that the copolymer A was changed to the copolymer C obtained in Production Example 3. No component precipitation or the like was observed. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
4.0 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name: “TEPIC-S”), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate as aliphatic epoxy ( 10.0 g from Daicel Corporation, trade name: “Celoxide 2021P”, and a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride as the acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: “Ricacid” MH-700G ”) 19.2 g was heated and stirred at 80 ° C. to make it uniform. To this was added 0.2 g of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator, and a liquid resin composition was obtained at 25 ° C. No component precipitation or the like was observed.
The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
3.0 g of copolymer A obtained in Production Example 1, 6.0 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name: “TEPIC-S”), and hexahydrophthalic anhydride as an acid anhydride And 11.2 g of a mixture of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: “Licacid MH-700G”) was heated and stirred at 80 ° C. to make it uniform. To this was added 0.1 g of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator to make it uniform. However, when the temperature reached 25 ° C., dissolved triglycidyl isocyanurate was precipitated, and a resin composition could not be obtained.

Comparative Example 3
10.0 g of copolymer A obtained in Production Example 1, 2.0 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name: “TEPIC-S”), and hexahydrophthalic anhydride as an acid anhydride And 8 g of a mixture of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: “Licacid MH-700G”) was heated and stirred at 80 ° C. to make it uniform. To this, 0.1 g of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) was added as a curing accelerator to make it uniform. However, when the temperature is 25 ° C., the fluidity of the resin composition is lost, and the resin composition cannot be applied onto the LED light emitting device.

  Cured products obtained by curing the resin composition of the present invention include optical semiconductors (LEDs, etc.) and optical resins (sealing agents, adhesives, sealing agents), flat panel displays (organic EL elements, etc.). It can be used for optical electronic members such as optical waveguides, optical communication lenses and optical films, resist materials, and the like.

Claims (7)

As an epoxy resin, the ratio of the repeating unit (A) represented by the following formula (I) is 40 to 80 mol%, and the ratio of the repeating unit (B) represented by the following formula (II) is 20 to 60 mol%. in a copolymer and 5 to 40 mass%, triglycidyl isocyanurates 5-20 wt% and
Resin composition containing 40 to 60% by weight of acid anhydride as a curing agent (however, hydrogenation rate of aromatic ring obtained by directly hydrogenating aromatic epoxy resin in said epoxy resin is 90 to 100% Excluding those containing 20 to 95% by weight of epoxy resin) .

(In the formula, R ¹ and R ³ are a hydrogen atom or a methyl group, and R ² is a cyclic aliphatic group.) The resin composition according to claim 1, wherein the epoxy resin contains 20% by mass or less of an aliphatic epoxy compound. The resin composition according to claim 1 or 2, wherein R ² is a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dicyclopentanyl group, or a substituted or unsubstituted isobornyl group.   The resin composition in any one of Claims 1-3 containing a hardening accelerator.   The sum total of the monomer corresponding to the repeating unit (A) and the monomer corresponding to the repeating unit (B) contained in the copolymer is 5% by weight or less. Resin composition.   The resin composition according to any one of claims 1 to 5, wherein the total amount of chlorine contained in the copolymer is 1.10% by weight or less. The optical-semiconductor sealing material which consists of a resin composition in any one of Claims 1-6.