JP2015168778A - Epoxy resin composition, optical semiconductor encapsulating agent, and optical semiconductor device - Google Patents

Abstract

Disclosed is an epoxy resin composition for sealing an optical semiconductor that can provide a cured product that is excellent in curing speed, excellent in light transmittance, and that does not yellow even when left at high temperature for a long time.
An epoxy resin composition containing the following components (A) to (C). (A) Component: An epoxy compound component comprising an epoxy compound obtained by oxidizing an unsaturated bond of tetrahydroindene and a glycidyl isocyanurate compound, (B) component: curing agent (C) component: curing acceleration Agent [selection figure] None

Description

  The present invention relates to an epoxy resin composition, an optical semiconductor encapsulant, and an optical semiconductor device. More specifically, the present invention relates to an epoxy resin composition, an optical semiconductor sealing agent, and an optical semiconductor device. An epoxy resin composition capable of giving a hard-to-change cured product, an optical semiconductor encapsulant comprising the epoxy resin composition, and an optical semiconductor element sealed with a cured product of the optical semiconductor encapsulant And an optical semiconductor device.

  A curable epoxy resin composition comprising an epoxy compound and a curing agent thereof provides a cured product having various characteristics such as excellent transparency, and is therefore widely used in various applications. Yes.

  Examples of applications of curable epoxy resin compositions include sealing for protecting optical semiconductor elements that are put into practical use as various indoor / outdoor display boards, image reading light sources, traffic signals, large display units, etc. Applications can be mentioned. In recent years, the output of optical semiconductor elements has been increased and the wavelength has been shortened, and materials that seal them are those that have excellent light transmission properties and do not easily yellow even when left at high temperatures for a long time. It is desired.

  Conventionally, a technique using a non-aromatic epoxy compound such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate as a main agent as a curable epoxy resin composition with little yellowing of a cured product It has been known. For example, Patent Document 1 discloses a resin composition for encapsulating a diode comprising 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and methylhexahydrophthalic anhydride as active ingredients. Yes.

  However, even when such a non-aromatic epoxy compound is used, yellowing is inevitable if the cured product is stored for several days at a high temperature (150 ° C.). It was difficult to obtain yellowing resistance required for a sealing material for a high-brightness optical semiconductor element. Furthermore, since 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate has an ester bond in the molecule, the ester group easily undergoes hydrolysis under the influence of moisture in the air, and the cured product There was also a problem of easily causing coloring.

  As means for solving such a problem, a curable epoxy resin composition containing an epoxy compound having no ester group in the molecule has been proposed. For example, Patent Document 2 and Patent Document 3 describe resin compositions obtained by blending an alicyclic diepoxy compound having a tetrahydroindene skeleton, an acid anhydride, and a curing accelerator.

JP 2000-196151 A International Publication No. 2012/137880 JP 2013-133339 A

  However, according to the study by the present inventors, the resin compositions as described in Patent Document 2 and Patent Document 3 require a long time for curing, and thus there is a problem that productivity of the cured product is deteriorated. In addition, when obtaining a thin film-like sealing material, such as when an optical semiconductor element is a surface-mounted element, the epoxy resin composition tends to be poorly cured due to volatilization or moisture absorption of the curing agent during curing. It became clear that it has. In addition, these resin compositions, compared to general curable epoxy resin compositions, have been prevented from yellowing, but are subjected to harsh conditions such as being irradiated with light for a long time at a high temperature. Then, yellowing was caused.

  Therefore, the present invention provides an epoxy resin composition that is excellent in curing speed, has excellent light transmittance, and can give a cured product that does not yellow even when irradiated with light for a long time at a high temperature. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have found that a curable epoxy using an alicyclic diepoxy compound having a tetrahydroindene skeleton and an epoxy compound having a triazine ring as an epoxy compound. When the resin composition is constituted, an epoxy resin composition having excellent curing speed, excellent light transmittance, and capable of giving a cured product that does not yellow even when irradiated with light at a high temperature for a long time. It was found that can be obtained. Furthermore, it discovered that this epoxy resin composition was used suitably as an optical semiconductor sealing agent. The present invention has been completed based on this finding.

（式中、Ｒ^１〜Ｒ^１２は、互いに独立して、水素原子、ハロゲン原子および炭素数１〜２０の炭化水素基から選択される基を表す。）で示されるエポキシ化合物（α）と、下記式（ＩＩ）

（式中、Ｒ^１３〜Ｒ^１５は、互いに独立して、水素原子、炭素数１〜２０の炭化水素基、エポキシ基含有基、およびエポキシ基含有基から誘導される基から選択される基を表し、Ｒ^１３〜Ｒ^１５のうちの少なくとも２つはエポキシ基含有基である。）で示されるエポキシ化合物（β）と、を含んでなるエポキシ化合物成分
（Ｂ）成分：硬化剤
（Ｃ）成分：硬化促進剤 Thus, according to the present invention, an epoxy resin composition containing the following components (A) to (C) is provided.
(A) component: following formula (I)

(Wherein R ^{1 to} R ¹² each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms); The following formula (II)

(In the formula, R ^{13 to} R ¹⁵ each independently represent a group selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an epoxy group-containing group, and a group derived from an epoxy group-containing group. And at least two of R ^{13 to} R ¹⁵ are epoxy group-containing groups), and an epoxy compound component (B) component: a curing agent (C) component : Curing accelerator

  In said epoxy resin composition, it is preferable that weight ratio (epoxy compound ((alpha)): epoxy compound ((beta))) of an epoxy compound ((alpha)) and an epoxy compound ((beta)) is 20: 80-80: 20. .

  Moreover, according to this invention, the optical-semiconductor sealing agent which consists of said epoxy resin composition is provided.

  Moreover, according to this invention, the optical semiconductor device provided with the optical semiconductor element sealed with the hardened | cured material of said optical semiconductor sealing agent is provided.

  According to the present invention, there is provided an epoxy resin composition that is excellent in curing speed, excellent in light transmittance, and capable of giving a cured product that does not yellow even when placed at a high temperature for a long time. Can do. And this epoxy resin composition can be used suitably as an optical semiconductor sealing agent.

The epoxy resin composition of the present invention contains the following components (A) to (C).
Component (A): Epoxy compound component (B) comprising the epoxy compound (α) represented by the formula (I) and the epoxy compound (β) represented by the formula (II): Curing agent ( C) Component: Curing accelerator

  The component (A) used as an essential component in the epoxy resin composition of the present invention includes the epoxy compound (α) represented by the formula (I), the epoxy compound (β) represented by the formula (II), Is an epoxy compound component.

The epoxy compound (α) is an alicyclic diepoxy compound having a tetrahydroindene skeleton. In formula (I) showing the structure of the epoxy compound (α), R ^{1 to} R ¹² each independently represents a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. . Examples of the halogen atom that can be a group represented by R ^{1 to} R ¹² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; And an alkylidene group having 2 to 20 carbon atoms such as a propylidene group. R ^{1 to} R ¹² are each independently a group selected from a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, Most preferably, all are hydrogen atoms. That is, tetrahydroindene diepoxide is most preferably used as the epoxy compound (α) represented by the formula (I).

  Although the epoxy equivalent of an epoxy compound ((alpha)) is not specifically limited, Usually, 76-200 g / equivalent, Preferably it is 76-100 g / equivalent.

  The epoxy compound (α) represented by the formula (I) can be produced by a conventionally known method. For example, as represented by the following formula (III), a method of oxidizing (epoxidizing) a cyclic olefin compound having a tetrahydroindene skeleton with an oxidizing agent can be mentioned.

R < ¹ > -R < ¹² > in Formula (III) represents the same group as Formula (I).

  Although the oxidizing agent used for the epoxidation reaction of the cyclic olefin compound represented by the formula (III) is not particularly limited, examples thereof include persulfates, hydrogen peroxide, aliphatic percarboxylic acids, and organic peroxides. it can. Moreover, although the usage-amount of an oxidizing agent is not specifically limited, It is an equimolar or more normally with respect to a cyclic olefin compound, Preferably it is 1-2 times mole.

  The epoxidation reaction is preferably performed in a solvent. The solvent to be used is not particularly limited, but aliphatic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as toluene; esters such as ethyl acetate and methyl acetate; alcohols such as methanol and ethanol; acetone and methyl ethyl ketone And ketones such as acetonitrile; and nitriles such as acetonitrile. These organic solvents and water can also be used in combination. In addition, when using an organic solvent and water together, when an organic phase and an aqueous phase are phase-separated to form a heterogeneous system, it is preferable to use a phase transfer catalyst. Although reaction temperature is not specifically limited, Usually, it is 0 degreeC or more and the boiling point or less of the solvent to be used, Preferably it is 20-70 degreeC. The reaction time may be determined according to the reaction scale and the like, and is not particularly limited, but is usually selected in the range of 10 minutes to 100 hours, preferably 1 to 50 hours. After completion of the reaction, the generated epoxy compound represented by the formula (I) is obtained by, for example, a method of precipitating with a poor solvent, a method of adding distilled water under stirring to distilling off the solvent, a direct desolvation method or the like. Can be recovered from the reaction solution.

  In the epoxy compound represented by formula (I), there are four stereoisomers based on the configuration of two epoxy rings, and any of these stereoisomers is used in the epoxy resin composition of the present invention. It is also possible to use a stereoisomer mixture in which these stereoisomers are present in an arbitrary ratio. However, from the viewpoint of obtaining an epoxy resin composition with more excellent transparency, the epoxy compound represented by the formula (I) is an exo-endo among four stereoisomers based on the configuration of two epoxy rings. The ratio of the total amount of the body and the end-end body is preferably 10% by weight or less, and more preferably 5% by weight or less. In addition, the ratio of this stereoisomer can be calculated | required based on the peak area ratio by a gas chromatography.

  In order to reduce the content of the exo-endo compound and the endo-endo compound in the epoxy compound represented by the formula (I), a method for separating these stereoisomers may be according to a conventional method, and is not particularly limited. However, column chromatography using, for example, precision distillation or silica gel as a filler can be applied.

The epoxy compound (β) is an epoxy compound having a triazine ring. In formula (II) showing the structure of the epoxy compound (β), R ^{13 to} R ¹⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an epoxy group-containing group, and an epoxy group-containing group. Represents a group selected from the group derived from R, and at least two of R ^{13 to} R ¹⁵ are epoxy group-containing groups. Examples of the hydrocarbon group having 1 to 20 carbon atoms that can be a group represented by R ^{13 to} R ¹⁵ include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a vinyl group, an allyl group, and the like And alkenyl groups having 2 to 20 carbon atoms; alkylidene groups having 2 to 20 carbon atoms such as ethylidene group and propylidene group; and the like. Moreover, as an epoxy group containing group, epoxy group (1,2-epoxyethyl group), glycidyl group (2,3-epoxypropyl group), 3,4-epoxybutyl group, 4,5-epoxypentyl group, 5 , 6-epoxyhexyl group, 6,7-epoxyhexyl group and the like. The group derived from the epoxy group-containing group is not particularly limited as long as it is a group obtained by reacting a modifier capable of reacting with the epoxy group-containing group. For example, an acid anhydride compound is reacted with the epoxy group. Mention may be made of the resulting diester groups. Further, it is preferable that all of R ^{13 to} R ¹⁵ are groups independently selected from an epoxy group-containing group and a group derived from an epoxy group-containing group, and further, independently of each other, a glycidyl group. And a group selected from a group derived from a glycidyl group. That is, as the epoxy compound (β) represented by the formula (II), tris- (2,3-epoxypropyl) -isocyanurate or a modified product thereof is more preferably used. However, since pure tris- (2,3-epoxypropyl) -isocyanurate has crystallinity and is inferior in handleability due to its crystallinity, it is easy to handle the epoxy compound (β). From the viewpoint of improving the quality, it is necessary to convert a part of the glycidyl group (2,3-epoxypropyl group) of tris- (2,3-epoxypropyl) -isocyanurate into a diester group with an acid anhydride. Particularly preferred. In addition, an epoxy compound ((beta)) may be used individually by 1 type, and can also use 2 or more types together.

Moreover, you may use an epoxy compound ((beta)) as a mixture with another compound, for example, two or more of R < ¹³ > -R < ¹⁵ > in Formula (II) are groups derived from an epoxy group containing group. What has become may be mixed together with the epoxy compound (β). In particular, when tris- (2,3-epoxypropyl) -isocyanurate is used as the epoxy compound (β), two or more glycidyl groups (2,3-epoxypropyl groups) are derived from the glycidyl group. What was converted into the group may be mixed together with the epoxy compound (β). However, if two or more glycidyl groups (2,3-epoxypropyl groups) are converted into groups derived from glycidyl groups, the resulting epoxy resin composition is likely to yellow. Therefore, the abundance thereof is preferably 20% by weight or less, and more preferably 15% by weight or less with respect to the epoxy compound (β).

  Although the epoxy equivalent of an epoxy compound ((beta)) is not specifically limited, Usually, it is 100-500 g / equivalent, Preferably it is 100-200 g / equivalent.

  The epoxy compound (β) represented by the formula (II) can be produced by a conventionally known method, and a commercially available product can also be used. As an epoxy compound (β), a commercially available product that is particularly preferably used is tris- (2,3-epoxypropyl) by reacting tris- (2,3-epoxypropyl) -isocyanurate with propionic anhydride. -“TEPIC PAS B26” or “TEPIC PAS” manufactured by Nissan Chemical Industries, Ltd., which is obtained by converting a part of glycidyl group (2,3-epoxypropyl group) of isocyanurate into 2,3-bis (propionyloxy) propyl group B22 ".

  In the epoxy compound component (component (A)) of the epoxy resin composition of the present invention, the weight ratio of the epoxy compound (α) to the epoxy compound (β) is not particularly limited, but epoxy compound (α): epoxy compound ( The value of β) is preferably 20:80 to 80:20, and more preferably 40:60 to 60:40. When the weight ratio of the epoxy compound (α) and the epoxy compound (β) is within this range, the resulting epoxy resin composition can give a cured product that is not particularly easily yellowed.

  The component (B) used as an essential component in the epoxy resin composition of the present invention is a curing agent. The curing agent has a reactive group that can react with the epoxy group of the epoxy compound by light, heat, etc., and the reactive group and the epoxy group of the epoxy compound react to cure and cure the epoxy compound component. If it is, it will not specifically limit, The various hardening | curing agents used as a hardening | curing agent for epoxy resins can be used, but it is liquid acid anhydride at 25 degreeC from a viewpoint of making the viscosity of a curable composition low enough. A material curing agent is preferably used. The acid anhydride curing agent which is liquid at 25 ° C. has one or two aliphatic rings or aromatic rings in the molecule, and one or two acid anhydride groups as reactive groups. Particularly preferred are acid anhydrides having 4 to 25 carbon atoms, preferably 8 to 20 carbon atoms. Specific examples of the compound suitably used as the acid anhydride curing agent include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, glutaric anhydride and the like. Can be mentioned. Of these, methylhexahydrophthalic anhydride is preferably used. These acid anhydride curing agents may be used singly or in combination of two or more.

  Further, as the curing agent, for example, acid anhydride curing agents that are solid at room temperature such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride can be used. When using an acid anhydride curing agent that is solid at room temperature, it is preferably dissolved in a liquid acid anhydride curing agent at 25 ° C. and used as a liquid mixture at room temperature. Examples of the curing agent particularly preferably used in the present invention include methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

  As the acid anhydride curing agent, commercially available products are available, and examples thereof include “Licacid MH-700”, “Licacid MH-700G”, “Licacid HNA-100” (manufactured by Shin Nippon Rika Co., Ltd.), Examples thereof include “HN-5500E”, “HN-7000” (manufactured by Hitachi Chemical Co., Ltd.), and glutaric anhydride (manufactured by Japan Epoxy Resin Co., Ltd.).

  Although the reactive group equivalent of a hardening | curing agent is not specifically limited, Usually, it is 100-300 g / equivalent, Preferably it is 150-200 g / equivalent.

  The amount of the curing agent in the epoxy resin composition of the present invention is not particularly limited, but the ratio of the number of moles of the group that reacts with the epoxy group of the curing agent to the number of moles of the epoxy group of the entire epoxy compound contained in the composition. However, what is necessary is just to determine the quantity of a hardening | curing agent so that it may become 0.5-2.0 normally, Preferably it is 0.8-1.2, Most preferably, it is 0.9-1.1. That is, if the amount of the curing agent is determined so that the ratio of the value obtained by dividing the weight of the curing agent by the reactive group equivalent to the sum of the values obtained by dividing the weight of each epoxy compound by the epoxy equivalent is within the above range. Good. By making the quantity of a hardening | curing agent into such a range, the epoxy resin composition obtained can be made excellent in especially a moldability and a cure rate.

  The component (C) used as an essential component in the epoxy resin composition of the present invention is a curing accelerator. The curing accelerator is not particularly limited as long as it accelerates the curing (crosslinking reaction) of the epoxy compound component (component (A)) by the curing agent (component (B)), and is used as a curing accelerator for epoxy resin. Various curing accelerators can be used.

  Specific examples of the curing accelerator include tertiary amine-based curing accelerators such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl Imidazole curing accelerators such as -4-methylimidazole and 1-benzyl-2-methylimidazole; organophosphorus curing accelerators such as triphenylphosphine and triphenyl phosphite; tetrabutylphosphonium diethyl phosphorodithioate, tetra Quaternary phosphonium salt curing accelerators such as phenylphosphonium bromide, methyltributylphosphonium dimethyl phosphate, and tetra-n-butylphosphonium bromide; 1,8-diazabicyclo [5.4.0] undecene-7 and the like Diazabicycloalkene curing accelerators such as salts; organometallic compound curing accelerators such as zinc octylate, tin octylate and aluminum acetylacetone complexes; quaternary ammonium salt curing accelerators such as tetraethylammonium bromide and tetrabutylammonium bromide Agents; boron compound-based curing accelerators such as boron trifluoride and triphenylborate; metal halide-based curing accelerators such as zinc chloride and stannic chloride; and the like.

  In addition, high melting point imidazole compounds, dicyandiamide, high melting point dispersion type latent accelerators such as amine addition type accelerators in which amine is added to epoxy resin, etc .; the surface of imidazole type, phosphorus type and phosphine type accelerators are coated with a polymer Microcapsule type latent accelerator; amine salt type latent curing accelerator; high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt; active energy rays such as ultraviolet rays and radiation It is also possible to use a latent curing accelerator typified by a photodissociation type photocationic polymerization type latent curing accelerator that generates protons. In addition, a hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

  The amount of the curing accelerator in the epoxy resin composition of the present invention is not particularly limited, but is usually 0.1 to 10 parts by weight, preferably 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the whole epoxy compound contained in the composition. 5 to 5 parts by weight.

  The epoxy resin composition of the present invention may contain other components as necessary in addition to the components (A) to (C). Examples of other components include reaction modifiers, discoloration inhibitors, epoxy compounds other than the epoxy compound (α) and the epoxy compound (β), and various additives.

  The reaction modifier is a compound that moderates the curing reaction of the epoxy resin composition. Known reaction modifiers can be used. Of these, polyhydric alcohol compounds are preferred.

  4 or more are preferable and, as for carbon number of a polyhydric alcohol compound, 4-10 are more preferable. The number of hydroxyl groups in the polyhydric alcohol compound is preferably 3 or more, more preferably 3 to 10. By using an epoxy resin composition containing a polyhydric alcohol compound having 4 or more carbon atoms and 3 or more hydroxyl groups, a cured product having more excellent heat resistance can be obtained. Specific examples of the polyhydric alcohol compound include ethylene glycol, diethylene glycol, glycerin, trimethylolpropane and the like. A polyhydric alcohol compound can be used individually by 1 type or in combination of 2 or more types. When the polyhydric alcohol compound is contained, the content thereof is usually 3 to 20 wt%, preferably 3 to 15 wt%, more preferably 3 with respect to the curing agent (component (B)) of the epoxy resin composition. -10% by weight.

  The discoloration preventing agent is a compound that prevents discoloration of the cured product. Examples of the discoloration preventing agent include phosphorus-based discoloration preventing agents, hindered phenol-based discoloration preventing agents, and thioether-based discoloration preventing agents. These discoloration inhibitors can be used alone or in combination of two or more.

  When the epoxy resin composition of the present invention contains a phosphorus-based discoloration inhibitor, the content thereof is usually 0.5% by weight or more, preferably 0.5 to the epoxy compound component (component (A)). 5% by weight.

  Specific examples of the epoxy compound other than the epoxy compound (α) and the epoxy compound (β) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD type epoxy resin. Resin; Novolac type epoxy resin such as phenol novolac type epoxy resin and orthocresol novolac type epoxy resin; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate Limonene diepoxide, epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis-3-cyclohexenyl methyl ester and its ε-caprolactone adduct, epoxidized butanetetraca Alicyclic epoxy resins other than epoxy compounds (α) such as tetrakis-3-cyclohexenyl methyl ester of boronic acid and its ε-caprolactone adduct; water such as hydrogenated bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin Examples thereof include hydrogenated bisphenol type epoxy resins; hydrogenated phenol novolac type epoxy resins, hydrogenated novolac type epoxy resins such as hydrogenated cresol novolac type epoxy resins; and heterocyclic-containing epoxy resins other than the epoxy compound (β). These other epoxy compounds can be used individually by 1 type or in combination of 2 or more types. In the epoxy resin composition of the present invention, the content of the epoxy compound other than the epoxy compound (α) and the epoxy compound (β) is not particularly limited, but is preferably 0 as a ratio to the total epoxy compounds in the epoxy resin composition. -50% by weight, more preferably 0-45% by weight.

  Additives include silicone-based and fluorine-based antifoaming agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, fillers, flame retardants, colorants, antioxidants (phenolic, phosphorus, Sulfur antioxidants, etc.), UV absorbers, phosphors, ion adsorbents, dyes, pigments, stress reducing agents, flexibility imparting agents, mold release agents, waxes, halogen trapping agents, leveling agents, wetting improvement Agents and the like. As long as the effect of the present invention is not impaired, the content of the additive is not particularly limited. The epoxy resin composition of the present invention may contain any amount of additives.

  The epoxy resin composition of the present invention can be prepared by stirring and mixing the components (A) to (C) described above and other components used as necessary according to a known method. Although the temperature at the time of stirring and mixing changes also with the components to mix | blend, it is preferable that it is about 10-80 degreeC. If the temperature at the time of preparation is too low, the viscosity may be too high and uniform stirring and mixing operations may be difficult. Conversely, if the temperature at the time of preparation is too high, a curing reaction will occur. This is not preferable because the viscosity of the composition may increase.

  When stirring or mixing, for example, a three roll, kneader, universal stirrer, ball mill, planetary mixer, homogenizer, homodisperser, or the like can be used.

  The epoxy resin composition of the present invention can provide a cured product that is excellent in curing speed, excellent in light transmittance, and hardly yellows even when placed at a high temperature for a long time. Therefore, the epoxy resin composition of the present invention is preferably used as a sealing agent, and particularly preferably used as an optical semiconductor sealing agent.

  The optical semiconductor sealing agent of the present invention comprises a cured product of the epoxy resin composition of the present invention and is used for the purpose of sealing an optical semiconductor element. When using the optical semiconductor sealing agent of the present invention, for example, to seal the optical semiconductor element, it is sealed with a sealing material by applying it to a predetermined place and then curing it by heating. An optical semiconductor device can be obtained.

  The method for applying the optical semiconductor sealing agent is not particularly limited, and for example, a roll coating method, a spray method, a dip method, or the like can be used. The heating temperature is usually 100 to 200 ° C, preferably 100 to 180 ° C, more preferably 100 to 150 ° C. The heating time is usually 1 to 24 hours, preferably 2 to 12 hours. In addition, if the curing reaction proceeds abruptly, there is a risk of inducing cracks due to internal stress. Therefore, it is preferable to change the heating temperature step by step. For example, generation of cracks can be suppressed by performing primary curing at 100 to 130 ° C. for about 1 to 3 hours and secondary curing at 130 to 180 ° C. for about 2 to 6 hours.

  Since the optical semiconductor encapsulant of the present invention has an excellent curing rate, an optical semiconductor device can be produced with high productivity, and it has excellent light transmittance and is hardly yellowed even when left at a high temperature for a long time. Is. Since it has these characteristics, the optical semiconductor sealing agent of this invention is useful as a sealing agent which seals the light-emitting body of an optical semiconductor element. Specifically, the photo-semiconductor encapsulant of the present invention is a light-emitting diode (LED), phototransistor, photo-diode, photo-coupler, charge-coupled device (CCD), EPROM, photo-sensor, etc. It is useful as a sealant for sealing.

  The optical semiconductor device of the present invention includes a light emitter including an optical semiconductor element sealed with a cured product of the optical semiconductor sealing agent of the present invention, and the sealing material of the present invention for sealing the light emitter. Is. Examples of the light emitter in this case include light emitters of optical semiconductor elements such as a light emitting diode (LED), a phototransistor, a photodiode, a photocoupler, a charge coupled device (CCD), an EPROM, and a photosensor. Since the optical semiconductor device of the present invention is an optical semiconductor element encapsulated with the optical semiconductor encapsulant of the present invention, it can be manufactured with good productivity, has high brightness, and is used for a long time. Even so, it is difficult to yellow.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

  Various measurements and evaluations were performed according to the following methods.

[Stereoisomer composition ratio of tetrahydroindene diepoxide]
It calculated based on the peak area ratio of the chart obtained by gas chromatography. In addition, the stereoisomer corresponding to each peak was identified by measurement of ¹ H-NMR and ¹³ C-NMM (see JP2013-72058A). Moreover, the measurement conditions of gas chromatography are as follows.
Measuring device: 7890A (manufactured by Agilent)
Column: HP-1 (manufactured by Agilent), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm
Liquid phase: 100% -dimethylpolysiloxane Carrier gas: Nitrogen carrier gas Flow rate: 1.0 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Temperature rising pattern (column): held at 50 ° C. for 10 minutes, temperature rising to 5 ° C./minute up to 250 ° C. Split ratio: 50
Sample: 0.5 μL

[Curing speed]
1 ml of the epoxy resin composition as a sample was placed on an iron plate heated to 120 ° C., and stretched into a circle having a diameter of about 50 mm with a glass rod. Then, while stirring the sample with a glass rod, the time (curing time) from when the sample started to melt until the sample hardened (gelled) and could not be stirred was measured. This measurement was performed three times for one type of sample, and the average value was evaluated according to the following criteria.
◯: Curing time is less than 15 minutes Δ: Curing time is 15 minutes or more and less than 30 minutes ×: Curing time is 30 minutes or more

[Formability]
The cured product obtained in each example was observed with the naked eye and evaluated according to the following criteria.
◯: A cured product is obtained, and voids and cracks are not observed in the cured product. Δ: A cured product is obtained, but voids and cracks are observed in the cured product. X: A cured product is not obtained.

[Yellowness and light transmittance (initial)]
The transmission spectrum of the cured product immediately after production as a sample was measured with an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, “V-570”), and the light transmittance at a wavelength of 400 nm was determined. Similarly, the yellowness of a cured product as a sample was measured with a spectral color difference meter (“SE-2000” manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the yellowness, the better the hue, and the higher the light transmittance, the better.

[Yellowness and light transmittance after heat and light resistance test]
The cured product immediately after production was placed on a hot plate set at 150 ° C., and this was irradiated with light from an LED (wavelength of about 450 nm, distance between the light source and the cured product) of 300 hours. Using this cured product as a sample, the light transmittance at a wavelength of 400 nm was determined in the same manner as in the previous section, and the yellowness was measured.

[Synthesis example (synthesis of tetrahydroindene diepoxide)]
In a three-necked reactor equipped with a thermometer, 40.0 g (0.333 mol) of 3a, 4,7,7a-tetrahydroindene was dissolved in 400 ml of acetone in a nitrogen stream, and further 201.3 g of sodium hydrogen carbonate. (2.396 mol) and 400 ml of distilled water were added. After cooling the obtained mixed liquid to 10 ° C. with a water bath, 327.4 g (0.532 mol) of a persulfate compound (manufactured by DuPont, “Oxone”) was added, and the liquid temperature of the reaction liquid was adjusted to 20-30 ° C. The mixture was stirred for 2 hours while adjusting the water bath temperature. Thereafter, the reaction solution was cooled to 0 ° C., 300 ml of a 10% aqueous sodium hydroxide solution, 300 ml of distilled water, and 300 ml of saturated brine were added, and extracted twice with 500 ml of n-hexane. The organic layer was collected, dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. The filtrate was concentrated using a rotary evaporator, and then the concentrate was vacuum-dried to obtain 41.5 g of a crude tetrahydroindene diepoxide (yield 82%). About this crude tetrahydroindene diepoxide, when the stereoisomer composition ratio was calculated | required, it was a stereoisomer composition ratio as shown in Table 1.

[Purification example (purification of tetrahydroindene diepoxide)]
40.1 g of the crude tetrahydroindene diepoxide obtained in the synthesis example was purified by vacuum distillation (vacuum degree 0.3 kPa) using a small high-speed rotation band type precision distillation apparatus (“HSB-605FF” manufactured by Toshin Seiki Co., Ltd.). did. When the stereoisomer composition ratio was calculated | required about the obtained refined tetrahydroindene diepoxide, it was a stereoisomer composition ratio as shown in Table 1.

[Example 1]
Obtained by reacting 50 parts of purified tetrahydroindene diepoxide (epoxy equivalent 80 g / equivalent) obtained in the purification example and 0.4 mole of propionic anhydride with 1 mole of tris- (2,3-epoxypropyl) -isocyanurate. Epoxy compounds (compounds represented by the following formulas (IV-1), (IV-2) and (IV-3)) in a molar ratio of the formulas (IV-1) :( IV-2) :( IV-3) = 60: 32: 8 content, manufactured by Nissan Chemical Industries, "TEPIC PAS B26", epoxy equivalent 130-140 g / equivalent) 50 parts, as a curing agent, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (Nippon Rika Co., Ltd., “Licacid MH-700G”, reactive group (anhydride group) equivalent 163 g / equivalent) 155 parts, tetrabutyl phosphate as a curing accelerator 1 part of honium diethyl phosphorodithioate (Nippon Chemical Industry Co., Ltd., “Hishicolin PX-4ET”) and 1 part of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) as reaction modifiers at 25 ° C. with a planetary mixer The epoxy resin composition of Example 1 was prepared by stirring for 10 minutes. About the epoxy resin composition of this Example 1, the cure rate was evaluated. The composition of the epoxy resin composition of Example 1 and the evaluation results of the curing rate are summarized in Table 2.

  Next, a pair of (two) glass substrates previously coated with a release film were laminated so as to form a 3 mm gap by interposing a spacer, and the epoxy resin of Example 1 obtained in this gap was obtained. The composition was injected. Next, the epoxy resin composition is semi-cured by heating in an oven at 120 ° C. for 2 hours, and further cured (completely cured) by heating in an oven at 150 ° C. for 4 hours to obtain a thickness. A cured product of Example 1 having a thickness of 3 mm was obtained. About the hardened | cured material of this Example 1, the moldability evaluation, the measurement of yellowness and light transmittance (initial stage), and the yellowness and light transmittance after a heat-resistant light-proof test were performed. Table 2 summarizes the moldability evaluation results, the yellowness and light transmittance (initial) measurement results, and the yellowness and light transmittance measurement results after the heat and light resistance test of the epoxy resin composition of Example 1. It was.

[Examples 2 to 4 and Comparative Examples 1 to 4]
Except having each changed the composition of the epoxy resin composition as shown in Table 2, it obtained the epoxy resin composition and hardened | cured material of Examples 2-6 and Comparative Examples 1-4 similarly to Example 1. And evaluated them. However, for the epoxy resin composition of Comparative Example 2, because the viscosity is too high and the moldability is poor, a cured product that can be used for measurement of yellowness and light transmittance (initial) cannot be obtained, These measurements could not be performed. The evaluation results of the epoxy resin compositions and cured products of Examples 2 to 4 and Comparative Examples 1 to 4 are summarized in Table 2. In Table 2, “TEPIC PAS B22” is an epoxy compound obtained by reacting 1 mol of tris- (2,3-epoxypropyl) -isocyanurate with 0.8 mol of propionic anhydride (formula (V -1), (V-2), (V-3) and (V-4) in the molar ratios of the formulas (V-1) :( V-2) :( V-3) :( V -4) = 35: 45: 17: 3, manufactured by Nissan Chemical Industries, “TEPIC PAS B22”, epoxy equivalent 180-200 g / equivalent), “Epolide GT401” is an alicyclic epoxy compound ( Butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, manufactured by Daicel, “Epolide GT401”, epoxy equivalent 200-240 g / equivalent) Kisaido 2021P "alicyclic epoxy compound (3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, Daicel Corporation," CELLOXIDE 2021P ", epoxy equivalent 128～145G / eq) is.

  As can be seen from Table 2, each of the epoxy resin compositions of Examples 1 to 4 corresponding to the epoxy resin composition of the present invention has a high curing rate, can be molded well, and has a small yellowness and a large light transmission. It can be said that the degree of deterioration in the heat and light resistance test is small. Therefore, the epoxy resin composition of the present invention can give a cured product that is excellent in curing speed, excellent in light transmittance, and hard to yellow even when irradiated with light at a high temperature for a long time. It can be said that it is a thing. On the other hand, the epoxy resin composition of Comparative Example 1 obtained using only tetrahydroindene diepoxide as an epoxy compound has a slow curing rate and causes yellowing when irradiated with light at a high temperature for a long time. It was. Moreover, the epoxy resin composition of Comparative Example 2 obtained using only “TEPIC PAS B26” corresponding to the epoxy compound (β) represented by the formula (II) as the epoxy compound has a too high viscosity, and is molded. The property was extremely bad. Moreover, as an epoxy compound, the epoxy resin compositions of Comparative Example 3 and Comparative Example 4 obtained by combining tetrahydroindene diepoxide with an epoxy compound other than the epoxy compound (β) represented by the formula (II) at high temperatures When irradiated with light for a long time, yellowing occurs, and the curing speed may be slow.

Claims (4)

The epoxy resin composition containing the following (A) component-(C) component.
(A) component: following formula (I)

(In the formula, R ^{1 to} R ¹² each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms.)
An epoxy compound (α) represented by
The following formula (II)

(In the formula, R ^{13 to} R ¹⁵ each independently represent a group selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an epoxy group-containing group, and a group derived from an epoxy group-containing group. And at least two of R ^{13 to} R ¹⁵ are epoxy group-containing groups.)
And an epoxy compound component (B) comprising: an epoxy compound component (β): a curing agent (C) component: a curing accelerator   The epoxy resin composition according to claim 1, wherein the weight ratio of the epoxy compound (α) to the epoxy compound (β) (epoxy compound (α): epoxy compound (β)) is 20:80 to 80:20.   An optical semiconductor sealing agent comprising the epoxy resin composition according to claim 1.   An optical semiconductor device comprising an optical semiconductor element sealed with a cured product of the optical semiconductor sealing agent according to claim 3.