JP5319567B2 - Epoxy resin composition for optical semiconductor device, cured product thereof, and optical semiconductor device obtained using the same - Google Patents

Description

  The present invention relates to an epoxy resin composition for an optical semiconductor device used for resin sealing of an optical semiconductor element such as a light emitting element or a light receiving element, a cured product thereof, and an optical semiconductor device obtained using the epoxy resin composition.

  Conventionally, as a resin composition for an optical semiconductor device used when resin-sealing in an optical semiconductor device having a light-emitting element, a light-receiving element, etc., transparency is required for a cured body that becomes a resin-sealed portion. Therefore, an epoxy resin composition obtained by using an epoxy resin such as a bisphenol A type epoxy resin and a curing agent such as an acid anhydride is widely used.

  However, in recent years, the brightness of light-emitting elements has been increasing, and on the other hand, the light-receiving sensor has become widespread as a pickup for in-vehicle applications and Blu-ray (registered trademark) disc compatible devices. There is a need for a sealing resin material having high performance.

  In the above epoxy resin composition for optical semiconductor devices, as a technique for improving heat resistance or light resistance, a technique for increasing the glass transition temperature (hereinafter also referred to as “Tg”) of a cured product obtained using a polyfunctional epoxy resin. In addition, a technique for suppressing light deterioration due to light absorption using an alicyclic epoxy resin (for example, see Patent Document 1) has been conventionally employed.

  Furthermore, an epoxy resin composition containing an acid anhydride and a polyester polyol in a specific mixing ratio is provided for the purpose of providing a sealing material excellent in heat resistance and transparency, and excellent in fracture toughness and crack resistance. It has been proposed to use (see Patent Document 2).

JP-A-5-32866 JP 2007-308683 A

  However, generally, as described above, when a polyfunctional epoxy resin, an alicyclic epoxy resin, or the like is used to improve heat resistance and light resistance, it causes a decrease in strength as a sealing resin. When the optical semiconductor element is resin-sealed, there is a possibility that a problem occurs in that the sealing resin cracks due to thermal contraction.

  Further, the epoxy resin composition of Patent Document 2 may cause a problem that sufficient light resistance cannot be obtained.

  The present invention has been made in view of such circumstances, and an epoxy resin composition for an optical semiconductor device, which is excellent in heat discoloration and light resistance, in which the occurrence of resin cracks during production of the optical semiconductor device is suppressed, and a cured product thereof. And an optical semiconductor device obtained using the same.

In order to achieve the above object, the present invention provides an epoxy resin composition for an optical semiconductor device containing the following components (A) to (E) , comprising a combination of the components (A) and (B): The ratio is 0.5 to 1.5 equivalents of the active group (an acid anhydride group or hydroxyl group) that can react with the epoxy group in the component (B) with respect to 1 equivalent of the epoxy group in the component (A). The content of the component (D) is 5 to 20% by weight of the entire resin component in the epoxy resin composition, and the content of the component (E) is 5 to 60% by weight of the entire epoxy resin composition. Let the epoxy resin composition for optical semiconductor devices be a 1st summary.
(A) An epoxy resin having two or more epoxy groups in one molecule.
(B) An acid anhydride curing agent.
(C) A curing accelerator.
(D) Polylactone polyol.
(E) Polyorganosiloxane represented by the following general formula (1) .
[Chemical formula 1]
R _m (OR ¹ ) _n SiO _{(4-mn) / 2} (1)
[In Formula (1), R is a C1-C18 substituted or unsubstituted saturated monovalent hydrocarbon group, and may be the same or different. R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. Further, m and n are each an integer of 0 to 3. ]

  Moreover, this invention makes the 2nd summary the epoxy resin composition hardening body for optical semiconductor devices formed by heat-curing the said epoxy resin composition for optical semiconductor devices.

  And this invention makes the 3rd summary the optical semiconductor device formed by resin-sealing an optical semiconductor element using the said epoxy resin composition for optical semiconductor devices.

That is, the present inventors effectively suppress the generation of cracks that occur when resin-sealing with a sealing material using polyfunctional epoxy resin or alicyclic epoxy resin, and are excellent in heat discoloration and light resistance. In order to obtain an epoxy resin composition for semiconductor devices, intensive studies were repeated. As a result, when combined polylactone polyol [component (D)] and a specific polyorganosiloxane [the component (E)] at a specific ratio, in addition to the flexibility possessed by the polylactone polyol, the specific poly The present invention finds that the excellent light resistance and heat resistance possessed by the organosiloxane are imparted, and that the synergistic effect of the combination of both imparts high heat discoloration and light degradation resistance, thereby achieving the intended purpose. Reached.

Thus, the present invention includes a polylactone polyol [(D) together with an epoxy resin [(A) component], an acid anhydride curing agent [(B) component], and a curing accelerator [(C) component]. Component] and a specific polyorganosiloxane [component (E)] in a specific ratio are epoxy resin compositions for optical semiconductor devices. For this reason, it becomes possible to form a transparent cured body that maintains a high glass transition temperature (Tg) and has excellent strength and flexibility, and that has excellent heat discoloration resistance and light resistance. can get. Therefore, by encapsulating an optical semiconductor element with this epoxy resin composition, an optical semiconductor device having excellent mechanical strength, heat resistance, and light resistance and having high reliability can be obtained.

Then, the content of the polylactone polyol is the component (D), since the range of 5 to 20% by weight of the total resin components in the epoxy resin composition, as well as provides a more further stress reduction, Glass A decrease in the transition temperature (Tg) is realized.

The content of the specific polyorganosiloxane is the (E) component, since the range of 5 to 60 wt% of the total epoxy resin composition, excellent in more heat discoloration resistance and light resistance, and tough A cured epoxy resin composition can be obtained.

The epoxy resin composition for optical semiconductor devices of the present invention (hereinafter also referred to as “epoxy resin composition”) comprises an epoxy resin (A component), an acid anhydride curing agent (B component), and a curing accelerator (C component). ), Polylactone polyol (component D), and a specific polyorganosiloxane (component E), usually in the form of a liquid or powder, or a tablet obtained by compressing the powder. It is used for the sealing material.

  As said epoxy resin (A component), it has 2 or more epoxy groups in 1 molecule, for example, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated naphthalene type epoxy resin Examples thereof include hydrogenated epoxy resins such as epoxy resins, and nitrogen-containing ring epoxy resins such as alicyclic epoxy resins, triglycidyl isocyanurates, and hydantoin epoxy resins. These may be used alone or in combination of two or more. Furthermore, you may use together with a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, a phenol novolac type epoxy resin, etc. Among these epoxy resins, it is preferable to use an alicyclic epoxy resin and triglycidyl isocyanurate alone or in combination from the viewpoint of transparency of the cured product and discoloration resistance.

  The epoxy resin (component A) may be solid or liquid at normal temperature, but in general, the epoxy resin used preferably has an average epoxy equivalent of 90 to 1,000. Preferably has a softening point of 160 ° C. or lower. That is, if the epoxy equivalent is too small, the cured epoxy resin composition may become brittle. Moreover, it is because the glass transition temperature (Tg) of an epoxy resin composition hardening body will become low when an epoxy equivalent is too large.

  Examples of the acid anhydride curing agent (B component) used together with the epoxy resin (component A) include, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, and tetrahydro anhydride. Examples thereof include phthalic acid, methyl nadic anhydride, nadic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. These may be used alone or in combination of two or more. Among these acid anhydride curing agents, it is preferable to use phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, or methylhexahydrophthalic anhydride alone or in combination. Further, the acid anhydride curing agent (component B) preferably has a molecular weight of about 140 to 200, and is preferably a colorless or light yellow acid anhydride curing agent.

The blending ratio of the epoxy resin (component A) and the acid anhydride curing agent (component B) is based on 1 equivalent of epoxy group in the epoxy resin (component A), and the acid anhydride curing agent (component B). It is necessary to set the active group (acid anhydride group or hydroxyl group) capable of reacting with the epoxy group in the inside to be 0.5 to 1.5 equivalents . More preferably, it is 0.7-1.2 equivalent. That is, when there are too few active groups, the curing rate of the epoxy resin composition becomes slow and the glass transition temperature (Tg) of the cured product tends to be low, and when there are too many active groups, moisture resistance decreases. This is because there is a tendency.

  Moreover, as said acid anhydride type hardening | curing agent (B component), according to the objective and use, the hardening | curing agent of other epoxy resins other than the said acid anhydride type hardening | curing agent, for example, a phenol type hardening | curing agent, an amine type | system | group Curing agents, those obtained by partial esterification of the above acid anhydride curing agents with alcohol, or curing agents for carboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, and methylhexahydrophthalic acid, alone or with the above acid You may use together with an anhydride type hardening | curing agent and a phenol type hardening | curing agent. For example, when a carboxylic acid curing agent is used in combination, the curing rate can be increased and the productivity can be improved. In addition, also when using these hardening | curing agents, the mixing | blending ratio should just follow the mixing | blending ratio (equivalent ratio) at the time of using the said acid anhydride type hardening | curing agent.

  Examples of the curing accelerator (C component) used together with the A component and the B component include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, tri-2,4,6- Tertiary amines such as dimethylaminomethylphenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o -Phosphorus compounds such as diethyl phosphorone dithioate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination of two or more. Among these curing accelerators, octylates or sulfonium salts of tertiary amines such as tri-2,4,6-dimethylaminomethylphenol are preferably used. Specifically, dimethylbenzylamine or the like is used.

  The content of the curing accelerator (component C) is preferably set to 0.01 to 8.0 parts by weight, more preferably 0.1 to 3 parts per 100 parts by weight of the epoxy resin (component A). 0.0 part by weight. That is, if the content of the curing accelerator is too small, a sufficient curing acceleration effect may not be obtained, and if the content of the curing accelerator is too large, the resulting cured product tends to be discolored. Because.

  The polylactone polyol (D component) used together with the components A to C is preferably a bi- or higher functional polycaprolactone polyol, and more specifically, polycaprolactone diol, polycaprolactone triol, and 4- or higher functional polycaprolactone. A polyol or the like can be used. These may be used alone or in combination of two or more.

  Among these polycaprolactone polyols, from the viewpoint of lowering stress and lowering the glass transition temperature (Tg), the molecular weight is preferably in the range of 300 to 2000, and the hydroxyl value is in the range of 80 to 500 (KOH · mg / g). Preferably there is. Among the polycaprolactone polyols, it is preferable to use polycaprolactone triol having the above physical properties, and as polycaprolactone triol further having the above physical properties, specifically, “Placcel 305” and “ “Placcel L320AL” or the like is preferably used.

Content of the said polylactone polyol (D component) needs to be set to the range of 5-20 weight% of the whole resin component in an epoxy resin composition . More preferably, it is 7 to 15% by weight. That is, if the content of the polylactone polyol (component D) is too small, there is a tendency that sufficient stress reduction and a sufficient lowering effect of the glass transition temperature (Tg) are difficult to obtain, and if the content is too large, This is because the glass transition temperature (Tg) is excessively decreased and thus the heat resistance tends to decrease.

Furthermore, in the present invention, a specific polyorganosiloxane (E component) is used together with the above-mentioned components A to D in order to improve light resistance and heat resistance.

The specific polyorganosiloxane (E component), since the epoxy resin (A component) and the molten mixture can be, polyorganosiloxane liquid is Ru is used in solid or ambient solventless. Thus, the polyorganosiloxane used in the present invention only needs to be capable of being uniformly dispersed in nano units in the cured epoxy resin composition.

Such polyorganosiloxane (E component), siloxane units as a polyorganosiloxane component of that is, those represented by the following general formula (1) are exemplified. In addition, a monovalent hydrocarbon group (R) having a hydroxyl group or an alkoxy group bonded to at least one silicon atom in one molecule, and 10 mol% or more of the monovalent hydrocarbon group (R) bonded to the silicon atom is a substituted or unsubstituted aromatic. The thing which is a hydrocarbon group is mention | raise | lifted.

[Chemical 2 ]
R _m (OR ¹ ) _n SiO _{(4-mn) / 2} (1)
[In Formula (1), R is a C1-C18 substituted or unsubstituted saturated monovalent hydrocarbon group, and may be the same or different. R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. Further, m and n are each an integer of 0 to 3. ]

  In the above formula (1), among R, which is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 18 carbon atoms, the unsubstituted saturated monovalent hydrocarbon group is specifically a methyl group, Ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, decyl A linear or branched alkyl group such as a group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a dicyclopentyl group, a decahydronaphthyl group, and an aromatic group such as a phenyl group, a naphthyl group, Aryl groups such as tetrahydronaphthyl group, tolyl group, ethylphenyl group, benzyl group, phenylethyl group, phenyl Group, aralkyl groups such as a methyl benzyl group.

  On the other hand, in R of the above formula (1), as the substituted saturated monovalent hydrocarbon group, specifically, a part or all of the hydrogen atoms in the hydrocarbon group are halogen atoms, cyano groups, amino groups, Examples thereof include those substituted by an epoxy group, and specifically include chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group, dibromophenyl group, Examples thereof include substituted hydrocarbon groups such as a difluorophenyl group, a β-cyanoethyl group, a γ-cyanopropyl group, and a β-cyanopropyl group.

And as said specific polyorganosiloxane (E component), what is preferable as R in said Formula (1) from the point of the affinity with the previous epoxy resin (A component) and the characteristic of the epoxy resin composition obtained. Is an alkyl group or an aryl group, and in the case of the above-mentioned alkyl group, more preferably those exemplified above as an alkyl group having 1 to 3 carbon atoms, and particularly preferred is a methyl group. A particularly preferred aryl group is a phenyl group. These groups selected as R in the formula (1) may be the same or different in the same siloxane unit or between siloxane units.

In the specific polyorganosiloxane (E component), in its structure represented by the above following formula (1), monovalent hydrocarbon groups bonded to silicon atoms (R), the 10 mol% or more aromatic It is preferably selected from hydrocarbon groups. That is, if there are too few aromatic hydrocarbon groups, since the affinity with the epoxy resin is insufficient, it becomes opaque when the polyorganosiloxane is dissolved and dispersed in the epoxy resin, and the resulting epoxy resin composition This is because even in the cured product, there is a tendency that sufficient effects cannot be obtained in terms of light resistance and physical properties. The content of such an aromatic hydrocarbon group is more preferably 30 mol% or more, and particularly preferably 40 mol% or more. In addition, the upper limit of content of the said aromatic hydrocarbon group is 100 mol%.

In the above formula (1), (OR ¹ ) is a hydroxyl group or an alkoxy group, and when (OR ¹ ) is an alkoxy group, as R ¹ , specifically, the alkyl exemplified above for R The group has 1 to 6 carbon atoms. More specifically, examples of R ¹ include a methyl group, an ethyl group, and an isopropyl group. These groups may be the same or different in the same siloxane unit or between siloxane units.

Further, the specific polyorganosiloxane (component E) has a hydroxyl group or alkoxy group bonded to at least one silicon atom in one molecule, that is, at least one of the siloxane units constituting the polyorganosiloxane is represented by the formula (1 It is preferable to have an (OR ¹ ) group. That is, when the hydroxyl group or alkoxy group is not present, the affinity with the epoxy resin is insufficient, and although the mechanism is not clear, the hydroxyl group or alkoxy group is in some form in the curing reaction of the epoxy resin. Although it is thought that it acts, it is difficult to obtain a cured product having sufficient physical properties formed by the resulting epoxy resin composition. In the specific polyorganosiloxane (component E), the amount of hydroxyl group or alkoxy group bonded to the silicon atom is preferably set in the range of 0.1 to 15% by weight in terms of OH group, and more Preferably it is 1 to 10% by weight. That is, when the amount of the hydroxyl group or alkoxy group is out of the above range, the affinity with the epoxy resin (component A) becomes poor, and particularly when it is too much (for example, more than 15% by weight), self-dehydration reaction or dealcoholization reaction This is because it may cause

  In the above formula (1), the repeating numbers m and n are each an integer of 0 to 3. The number of repetitions m and n that can be taken is different for each siloxane unit. The siloxane units constituting the polyorganosiloxane will be described in more detail. The following general formulas (2) to (5) ) Units represented by A1 to A4.

[Chemical 3 ]
A1 unit: (R) ₃ SiO _1/2 (2)
A2 unit: (R) ₂ (OR ¹ ) _n SiO _{(2-n) / 2} (3)
[In Formula (3), n is 0 or 1. ]
A3 unit: (R) (OR ¹ ) _n SiO _{(3-n) / 2} (4)
[In Formula (4), n is 0, 1 or 2. ]
A4 unit: (OR ¹ ) _n SiO _{(4-n) / 2} (5)
[In Formula (5), n is an integer of 0-3. ]
[In the above formulas (2) to (5), R is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be the same or different. R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. ]

  That is, in m of the formula (1), when m = 3, the A1 unit represented by the formula (2) is represented, and when m = 2, the A2 unit represented by the formula (3) is represented by m. The case of = 1 corresponds to the A3 unit represented by the above formula (4), and the case of m = 0 corresponds to the A4 unit represented by the above formula (5). Among these, the A1 unit represented by the above formula (2) is a structural unit that comprises only one siloxane bond and constitutes a terminal group, and the A2 unit represented by the above formula (3) has n of In the case of 0, it is a structural unit having two siloxane bonds and constituting a linear siloxane bond, and in the case where n is 0 in the A3 unit represented by the above formula (4), and the above formula (5) When n is 0 or 1 in the A4 unit represented by the formula, it is a structural unit that can have 3 or 4 siloxane bonds and contributes to a branched structure or a crosslinked structure.

Furthermore, in the specific polyorganosiloxane (component E), the constituent ratio of each of the A1 to A4 units represented by the above formulas (2) to (5) is set to the following ratios (a) to (d). It is preferable that
(A) 0 to 30 mol% of A1 unit
(B) A2 unit is 0 to 80 mol%
(C) A3 unit is 20 to 100 mol%
(D) A4 unit is 0-30 mol%

  More preferably, the A1 unit and the A4 unit are 0 mol%, the A2 unit is 5 to 70 mol%, and the A3 unit is 30 to 100 mol%. That is, by setting the constituent ratio of each of the A1 to A4 units in the above range, it is more preferable because an effect that appropriate hardness and elastic modulus can be imparted (maintained) to the cured body can be obtained.

The specific polyorganosiloxane (E component) is one in which the above structural units are bonded to each other or continuously, and the degree of polymerization of the siloxane units is in the range of 6 to 10,000. preferable. The properties of the specific polyorganosiloxane (E component) vary depending on the degree of polymerization and the degree of crosslinking, and may be either liquid or solid.

The specific polyorganosiloxane (E component) having such a siloxane unit represented by the formula (1) can be produced as follows. For example, it can be obtained by a reaction such as hydrolysis of at least one of organosilanes and organosiloxanes in the presence of a solvent such as toluene. In particular, a method of hydrolytic condensation of organochlorosilanes or organoalkoxysilanes is generally used. Here, the organo group is a group corresponding to R in the formula (1) such as an alkyl group or an aryl group. The A1 to A4 units represented by the above formulas (2) to (5) have a correlation with the structure of silanes used as raw materials. For example, in the case of chlorosilane, when triorganochlorosilane is used, the above formula (2 When the A1 unit represented by formula (3) uses diorganodichlorosilane, the A2 unit represented by formula (3) uses the organochlorosilane, and the A3 unit represented by formula (4) represents tetrachlorosilane. When used, A4 units represented by the formula (5) are obtained. In the above formulas (1) and (3) to (5), the substituent of the silicon atom shown as (OR ¹ ) is a hydrolysis residue that has not been condensed.

When the specific polyorganosiloxane (component E) is solid at room temperature, the softening point (pour point) is preferably 150 ° C. or lower from the viewpoint of melt mixing with the epoxy resin composition, Especially preferably, it is 120 degrees C or less.

Content of the said polyorganosiloxane (E component) needs to set to the range of 5 to 60 weight% of the whole epoxy resin composition . Particularly preferably, it is in the range of 10 to 40% by weight in consideration of an increase in the linear expansion coefficient. That is, when the content of the E component is too small, the heat resistance and light deterioration resistance tend to be reduced, and when the content of the E component is too large, the brittleness of the resulting cured epoxy resin composition itself is significant. This is because there is a tendency to become.

  Furthermore, in addition to the above components A to E, the epoxy resin composition of the present invention includes, as necessary, an antioxidant, a modifier, a silane coupling agent, a defoaming agent, a leveling agent, a release agent, a dye, Various additives such as pigments, phosphors, glass powders, titanium oxides, and silver particles can be appropriately blended.

  Examples of the antioxidant include antioxidants such as phenol compounds, amine compounds, organic sulfur compounds, and phosphine compounds. Examples of the modifying agent include various modifying agents such as glycols, silicones, and alcohols. As said silane coupling agent, various silane coupling agents, such as a silane type and a titanate type, are used, for example. Moreover, as said defoaming agent, various defoaming agents, such as a silicone type, are mention | raise | lifted, for example.

  The epoxy resin composition of the present invention can be produced, for example, as follows. That is, the above components A to E, and various additives as necessary are blended as appropriate, and then kneaded and melt mixed using a kneader. Next, this is cooled and solidified to room temperature, and pulverized via an aging step, whereby a powdery epoxy resin composition can be produced. Furthermore, if necessary, the powdery epoxy resin composition can be tableted to form a tablet.

  The epoxy resin composition of the present invention thus obtained can be used as a sealing material for optical semiconductor elements such as light emitting diodes (LEDs), various sensors, and charge coupled devices (CCDs). It is also possible to use it as a reflector forming material such as a reflector.

  An optical semiconductor device using the epoxy resin composition of the present invention can be produced by, for example, resin-sealing an optical semiconductor element using various molding methods such as ordinary transfer molding and casting. In this way, an optical semiconductor device in which the optical semiconductor element is resin-sealed is obtained. The molding conditions (curing conditions for the epoxy resin composition) include, for example, 130-180 ° C. × 2-8 minutes after heat curing and 130-180 ° C. × 1-5 hours post-curing.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

  First, each component shown below was prepared prior to the preparation of the epoxy resin composition.

〔Epoxy resin〕
Triglycidyl isocyanurate (melting point: 100 ° C., epoxy equivalent: 100 g / eq)

[Acid anhydride]
Mixture of 3-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 3: 7 (weight ratio) (acid equivalent: 168 g / eq)

[Curing accelerator]
Dimethylbenzylamine

[Modifier]
Denaturant a: manufactured by Daicel Chemical Industries, Plaxel 305
Denaturant b: Daicel Chemical Industries, Plaxel L320AL
Denaturing agent c: ethylene glycol

[Polyorganosiloxane e1]
206 g (50 mol%) of phenyltrimethoxysilane and 126 g (50 mol%) of dimethyldimethoxysilane were charged into the flask, and a mixture of 1.2 g of 20% HCl aqueous solution and 40 g of water was added dropwise thereto. After completion of the dropwise addition, refluxing was continued for 1 hour. Subsequently, after cooling to room temperature (25 degreeC), the solution was neutralized with sodium hydrogencarbonate. The obtained organosiloxane solution was filtered to remove impurities, and then a low-boiling product was distilled off under reduced pressure using a rotary evaporator to obtain a liquid polyorganosiloxane e1. The obtained polyorganosiloxane e1 contained 6% by weight of a hydroxyl group (OH group). Furthermore, the resulting polyorganosiloxane e1, the A2 unit 5 0 mol%, the unit A3 from 5 0 mol%, 60% phenyl, 40% methyl group, OH group contains 6 wt% It was a thing.

[Polyorganosiloxane e2]
A mixture of 182.5 g (90 mol%) of methyltrichlorosilane, 17.5 g (10 mol%) of dimethyldichlorosilane and 215 g of toluene was vigorously stirred in a mixed solvent of 550 g of water, 150 g of methanol and 150 g of toluene prepared in advance in the flask. It was added dropwise over 5 minutes. The temperature in the flask rose to 75 ° C., and stirring was continued for 10 minutes. This solution was allowed to stand, cooled to room temperature (25 ° C.), the separated aqueous layer was removed, water was then mixed, stirred and left to stand, and the water layer was removed. This was done until neutral. The remaining organic layer was refluxed for 30 minutes, and a part of water and toluene was distilled off. The obtained toluene solution of organosiloxane was filtered to remove impurities, and the remaining toluene was distilled off under reduced pressure using a rotary evaporator to obtain solid polyorganosiloxane e2. The obtained polyorganosiloxane e2 contained 6% by weight of a hydroxyl group (OH group). The raw material chlorosilane used had all reacted, and the obtained polyorganosiloxane e2 was composed of 10 mol% of the A2 unit, 90 mol% of the A3 unit, and 100% of the methyl group. .

〔Antioxidant〕
Made by Mitsui Chemicals, Sanko Epoch Clean

[Examples 1-8, Comparative Examples 1-5]
The components shown in Tables 1 and 2 to be described later were blended and kneaded in the proportions shown in the same table, and melt mixed. Subsequently, after aging, the target powdery epoxy resin composition was produced by cooling to room temperature, solidifying and pulverizing.

  Using the epoxy resin compositions of Examples and Comparative Examples thus obtained, various properties were evaluated according to the following methods. The results are also shown in Tables 1 and 2 below.

(Light transmittance)
Using each of the above epoxy resin compositions, a test piece having a thickness of 1 mm was prepared under predetermined curing conditions (conditions: 150 ° C. × 4 minutes molding + 150 ° C. × 3 hours cure), and this test piece (cured body) was used. Then, it was measured during liquid paraffin immersion. A spectrophotometer UV3101 manufactured by Shimadzu Corporation was used as the measuring device, and the light transmittance at a wavelength of 400 nm was measured at room temperature (25 ° C.).

[Glass transition temperature (Tg)]
Using each of the epoxy resin compositions described above, 10 to 20 mg of a cured body was produced under predetermined curing conditions (conditions: 150 ° C. × 4 minutes molding + 150 ° C. × 3 hours curing). And using this hardening body, it measured with the temperature increase rate of 10 degree-C / min with the differential scanning calorimeter (the Perkin Elmer company make, PYRIS1), and measured the glass transition temperature (Tg).

[Bending strength and deflection]
Using each of the above epoxy resin compositions, a test piece having a length of 90 mm, a width of 10 mm and a thickness of 4 mm was prepared under predetermined curing conditions (conditions: 150 ° C. × 4 minutes molding + 150 ° C. × 3 hours curing). And using this test piece (hardened body), according to JISK6911, the bending strength and the amount of deflection | deviations were measured by the speed | rate of 64 mm of distance between fulcrums, and 5 mm / min by the autograph made from Shimadzu Corporation.

[Light resistance life]
Using each of the above epoxy resin compositions, a test piece having a thickness of 1 mm was produced under predetermined curing conditions (conditions: 150 ° C. × 4 minutes molding + 150 ° C. × 3 hours cure). The test piece (cured body) is irradiated with a short wavelength laser (NDHV 310APC, manufactured by Nichia Chemical Co., Ltd.) with a wavelength of 405 nm at 25 mW at 20 μm (80 W / mm ² ), and the light obtained through the cured body is transmitted. The intensity was measured by receiving light with a power meter (manufactured by Coherent, OP-2VIS). As a result, the time (minutes) required for the received light intensity to reach 50% of the initial value was measured, and the measurement result was evaluated as the light fastness.

  From the above results, all the examples had high light transmittance, excellent transparency, high bending strength, large deflection, and long light resistance life.

  On the other hand, Comparative Example 1 in which no modifier was used had a long light resistance life, but had a low bending strength and a small amount of deflection. In Comparative Example 2, polyorganosiloxane was not used, and ethylene glycol, which is not a polylactone polyol, was used as a modifier. Therefore, there was no problem with respect to the measurement results of light transmittance, bending strength, and deflection amount. Was extremely short and inferior in light deterioration resistance. Comparative Example 3 uses polyorganosiloxane and uses ethylene glycol, which is not a polylactone polyol, as a modifier, so there was no problem with the measurement results of light transmittance, bending strength, and amount of deflection, but the light resistance life was The result was short and inferior in light resistance. In Comparative Example 4, polyorganosiloxane was used and a large amount of ethylene glycol that was not a polylactone polyol was used, so that the bending strength was low and the amount of deflection was small. Moreover, the light-resistant lifetime was also a short evaluation result. In Comparative Example 5, although polylactone polyol was used, polyorganosiloxane was not used, and thus the evaluation result was that the light resistance life was short.

[Production of optical semiconductor devices]
Next, the optical semiconductor device was manufactured using each powdery epoxy resin composition which is the product of the above example. That is, transfer molding (molding at 150 ° C. for 4 minutes, post-curing at 150 ° C. for 3 hours) using a special mold is performed using each of the epoxy resin compositions (example products), and an optical semiconductor element (SiN photodiode). : 1.8 mm × 2.3 mm × thickness 0.25 mm) was resin-sealed to produce a surface-mount type optical semiconductor device. This surface-mount type optical semiconductor device has an 8-pin small outline package [SOP-8: 4.9 mm × 3.9 mm × thickness 1.5 mm, lead frame: silver alloy layer (thickness) on the entire surface of a 42 alloy alloy body. 0.5 μm)]. The obtained optical semiconductor device was good because no crack was formed in the resin-encapsulated portion.

  The epoxy resin composition of the present invention is useful as a sealing material for optical semiconductor elements such as light emitting diodes (LEDs), various sensors, and charge coupled devices (CCDs), and further, for forming reflectors such as the above-mentioned LED reflectors. It can also be used as a material.

Claims (4)

An epoxy resin composition for an optical semiconductor device containing the following components (A) to (E), wherein the blending ratio of the component (A) and the component (B) is 1 equivalent of the epoxy group in the component (A) On the other hand, the active group (acid anhydride group or hydroxyl group) capable of reacting with the epoxy group in component (B) is 0.5 to 1.5 equivalents, and the content of component (D) is the epoxy resin composition. 5 to 20% by weight of the total resin component in the product, and the content of the component (E) is 5 to 60% by weight of the entire epoxy resin composition. .
(A) An epoxy resin having two or more epoxy groups in one molecule.
(B) An acid anhydride curing agent.
(C) A curing accelerator.
(D) Polylactone polyol.
(E) Polyorganosiloxane represented by the following general formula (1) .
[Chemical formula 1]
R _m (OR ¹ ) _n SiO _{(4-mn) / 2} (1)
[In Formula (1), R is a C1-C18 substituted or unsubstituted saturated monovalent hydrocarbon group, and may be the same or different. R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. Further, m and n are each an integer of 0 to 3. ] The epoxy resin composition for an optical semiconductor device according to claim 1 , wherein the content of the component ( C ) is 0.01 to 8.0 parts by weight with respect to 100 parts by weight of the component (A) . A cured epoxy resin composition for an optical semiconductor device, which is obtained by heat-curing the epoxy resin composition for an optical semiconductor device according to claim 1 or 2 . An optical semiconductor device obtained by resin-sealing an optical semiconductor element using the epoxy resin composition for an optical semiconductor device according to claim 1 or 2 .