JP2011094020A - Epoxy resin composition for sealing optical semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing optical semiconductor elements, excellent in the thermal stability of optical transmission and in crack resistance to thermal shock. <P>SOLUTION: The epoxy resin composition for sealing the optical semiconductor elements includes an epoxy resin (A), an epoxy-modified organopolysiloxane (B) of formula (1) [wherein, R<SP>1</SP>is H or alkyl; (a) and (b) are each an integer of 1 to 100 in a (a)/(b) ratio of 0.1 to 10; (m) is an integer of 1 to 50; R<SP>2</SP>is alkylene or oxyalkylene; R<SP>3</SP>is alkyl]; polyethylene glycol (C) having a number-average mol. wt. of 106 to 414, a polyol (D), and an alkoxyl group-having polysiloxane compound (E) as essential components. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for sealing an optical semiconductor element. More specifically, the present invention relates to an optical semiconductor device formed by curing an epoxy resin composition for optical semiconductor element sealing and sealing the optical semiconductor element.

Conventionally, in an optical semiconductor device, an optical semiconductor element such as a light emitting diode or a photodiode is sealed with an epoxy resin composition.
As the resin composition for sealing, as the optical semiconductor device itself is reduced in size and size, and has a wide variety of shapes, it has a curing stability such as that the physical properties of the cured resin can be stably expressed regardless of the shape. It has been demanded. The amount of heat generated from the optical semiconductor element has increased with the recent increase in the output power of the LED and the increase in the size of the optical semiconductor element itself. Therefore, the thermal stability of light transmission at a higher temperature and the high performance of the optical semiconductor element are high. Adhesion is required.
In addition, a highly reliable sealing resin is highly desired, for example, a crack is not generated in the sealing resin due to a thermal shock accompanying a change in use temperature of the optical semiconductor device.

As a general sealing resin composition, one using an alicyclic epoxy resin as a matrix component and an acid anhydride as a curing agent is known (for example, Patent Document 1).
However, due to miniaturization and thinning of the optical semiconductor device, the volatilization of the acid anhydride, which is a curing agent, cannot be ignored, and depending on the shape of the optical semiconductor device, the physical properties of the cured resin cannot be expressed stably. there were.

As a curing system for an epoxy resin having no acid anhydride, cationic curing of an epoxy resin is known (for example, Patent Document 2).
For cationic curing of epoxy resins, antimony-based thermal acid generators, which are practically strong acids, are used because of their low cationic curability, and the thermal stability of light transmission of the cured product is low. Further, when an alicyclic epoxy resin having a relatively high cationic polymerization property is used as a matrix resin, there is a problem that the cured product is brittle and has low crack resistance.

On the other hand, a sealing resin composition has been proposed in which an epoxy resin having a siloxane skeleton having high thermal stability of light transmission of a cured product is matrixed (for example, Patent Document 3).
However, the cured product has a problem that adhesion between the optical semiconductor element and the like is low, and peeling occurs between the resin and the optical semiconductor.

JP 2003-40972 A JP 2007-169337 A Japanese Patent Laid-Open No. 2007-9086

  Accordingly, an object of the present invention is to provide a resin composition for encapsulating an optical semiconductor element that is excellent in thermal stability of light transmission, crack resistance against thermal shock, and adhesion.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the epoxy resin composition for sealing an optical semiconductor element of the present invention includes an epoxy resin (A), an epoxy-modified organopolysiloxane (B) having a chemical structure represented by the general formula (1), and a number average molecular weight of 106 to An epoxy resin composition for encapsulating an optical semiconductor element, comprising 414 polyethylene glycol (C), polyol (D), and a polysiloxane compound (E) having one or more alkoxyl groups as essential components. .

[In General Formula (1), each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b are each independently an integer of 1 to 100, and a / b is 0.1 -10. m is an integer of 1-50. The bond form in [] may be either random bond, block bond, or a combination thereof. R ² is an alkylene group or an oxyalkylene group. R ³ is each independently an alkyl group having 1 to 6 carbon atoms. ]

  The epoxy resin composition of the present invention exhibits the effect that the cured product exhibits excellent high light transmission thermal stability, adhesion, and crack resistance against thermal shock. In addition, when the epoxy resin composition of the present invention is cured on an adherend such as a substrate or a film, warpage due to the cured product is small, so that the sealing of an optical semiconductor such as an ultraviolet light emitting element and the electronic material Suitable for coatings, adhesives, sealing materials and the like.

  In addition to the epoxy resin (A), the epoxy resin composition for sealing an optical semiconductor element of the present invention includes an epoxy-modified organopolysiloxane (B) having a specific chemical structure, and a polyethylene glycol (C) having a specific number average molecular weight. , A polyol (D), and a polysiloxane compound (E) having one or more alkoxyl groups as essential components.

  Examples of the essential epoxy resin (A) of the present invention include aromatic epoxy resin (A1), heterocyclic epoxy resin, (A2) aliphatic epoxy resin (A3), and alicyclic epoxy resin (A4). .

  Examples of the aromatic epoxy resin (A1) include polyglycol glycidyl ether (A11), glycidyl aromatic polyamine (A12), and other aromatic epoxy resins (A13).

  Examples of polyglycol glycidyl ether (A11) include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetra Chlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'- Dihydroxybiphenyl diglycidyl ether, phenol novolac resin Or glycidyl ether of cresol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, polyglycidyl of polyphenol obtained by condensation reaction of phenol with glioxal, glutaraldehyde or formaldehyde Examples include ethers, polyglycidyl ethers of polyphenols obtained by condensation reaction of resorcin and acetone.

  Examples of the glycidyl aromatic polyamine (A12) include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like.

  Other aromatic epoxy resins (A13) include diglycidyl urethane compounds obtained by addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, glycidyl group-containing polyurethane (pre) polymer, and bisphenol A alkylene oxide (ethylene oxide or propylene). Oxide) adduct diglycidyl ether and the like.

  An example of the heterocyclic epoxy resin (A2) is trisglycidylmelamine.

  Examples of the aliphatic epoxy resin (A3) include polyglycidyl ether (A31) of aliphatic polyhydric alcohol, polyglycidyl ester (A32) of fatty acid polycarboxylic acid, and glycidyl aliphatic amine (A33).

Examples of the polyglycidyl ether (A31) of aliphatic polyhydric alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane. Examples include triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, and the like.
Diglycidyl adipate is mentioned as a polyglycidyl ester body (A32) of fatty acid polyvalent carboxylic acid.

Examples of the glycidyl aliphatic amine (A33) include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
In the present invention, the aliphatic epoxy resin also includes a (co) polymer of glycidyl (meth) acrylate.

Examples of the alicyclic epoxy resin (A4) include an epoxy resin containing an alicyclic group in the molecule.
For example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, etc. It is done.
The alicyclic epoxy resin also includes a hydrogenated aromatic epoxy resin, such as a glycidyl ether of a polyhydric phenol nuclear hydrogenated product (such as a glycidyl ether of hydrogenated bisphenol A). It is done.

Among the alicyclic epoxy resins (A4), preferred are 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, and glycidyl ethers of polyhydric phenol nuclear hydrogenated products.
The nuclear hydrogenated product preferably has a hydrogenation rate of 90% or more.

  Of these epoxy resins (A), alicyclic epoxy resins (A4) are preferred from the viewpoint of thermal stability of light transmission of the cured epoxy resin.

Any epoxy resin (A) in the present invention can be used as long as it has two or more epoxy groups in the molecule, but preferably has 2 to 5 in the molecule.
The epoxy equivalent of the epoxy resin (A) is usually 80 to 5,000 g / eq, and preferably 100 to 2000 g / eq. The epoxy resin (A) may be used alone or in combination of two or more.

  The second essential component of the epoxy-modified organopolysiloxane (B) in the present invention is represented by the general formula (1).

[In General Formula (1), each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b are each independently an integer of 1 to 100, and a / b is 0.1 -10. m is an integer of 1-50. The bond form in [] may be either random bond, block bond, or a combination thereof. R ² is an alkylene group or an oxyalkylene group. R ³ is each independently an alkyl group having 1 to 6 carbon atoms. ]

R ¹ in the general formula (1) are each independently a hydrogen atom or a carbon atoms is an alkyl group having 1 to 6.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, and 3-methylbutyl group. , Neopentyl group, hexyl group, 2-ethylbutyl group and the like.

Among these, from the viewpoint of thermal stability of light transmission of the cured epoxy resin, a linear alkyl group is preferable, and a linear alkyl having 1 to 3 carbon atoms is more preferable. The plurality of R ¹ may all be the same or different.

R ² in the general formula (1) is an alkylene group or an oxyalkylene group.
Examples of the alkylene group include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a butylene group, and a hexylene group.
Examples of the oxyalkylene group include an alkylene group having 1 to 10 carbon atoms, such as an oxymethylene group, an oxyethylene group, and an oxypropylene group.

Among R ² , the alkylene group and oxyalkylene group having 1 to 7 carbon atoms are preferable from the viewpoint of crack resistance against thermal shock, and the alkylene group and oxyalkylene having 2 to 5 carbon atoms are more preferable. It is a group.

R < ³ > in General formula (1) is a hydrogen atom or a C1-C6 alkyl group each independently.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, and 3-methylbutyl group. , Neopentyl group, hexyl group, 2-ethylbutyl group and the like.

Among these, from the viewpoint of thermal stability of light transmission of the cured epoxy resin, a linear alkyl group is preferable, and a linear alkyl having 1 to 3 carbon atoms is more preferable.
The plurality of R ³ may all be the same or different.

In the general formula (1), a and b are each independently an integer of 1 to 100, and the ratio a / b is 0.1 to 10.
That a is 1-100 has having 1-100 epoxy group containing groups in the side chain of a molecule | numerator at least.
When a is 0, that is, when it does not have an epoxy group, an epoxy resin composition using it is not preferable because it is inferior in crack resistance against thermal shock and has low adhesion.
a and b are each preferably an integer of 1 to 50, more preferably from the viewpoint of crack resistance and moisture resistance against thermal shock, and compatibility with the epoxy resin (A) or polyol (D), and more preferably , A is 2-10, b is 2-20. Moreover, when a and b are in this range, the viscosity of (B) is not too high and is easy to handle.

  Furthermore, a / b is 0.1 / 10 normally, is 0.1-4, More preferably, it is 0.2-2, More preferably, it is 0.3-1. Within this range, the crack resistance against thermal shock is high.

  The bonding mode in [] in the general formula (1) represents random bonding, block bonding, or a combination thereof. From the viewpoint of elastic modulus, a random bond is preferable.

M in General formula (1) is an integer of 1-50. Preferably it is 1-20, More preferably, it is 1-10. Within this range, the viscosity of (B) is not too high and is easy to handle.

  The epoxy-modified organopolysiloxane (B) in the present invention can be produced by a known method and is not particularly limited. For example, a method in which an olefin group-containing siloxane is oxidized with a peroxide, a method in which a siloxane that has been previously Grignarded with magnesium bromide or the like is treated with an alkali together with epichlorohydrin, and a chlorosilane or acetoxysilane compound is reacted with glycidol to produce a glycidyl silicone ether. (For example, US Pat. No. 2,730,532 pamphlet), a method of reacting an ethylenically unsaturated group-containing epoxide and an organohydrogenpolysiloxane (for example, JP-A-7-133351), and the like.

  The number average molecular weight of the epoxy-modified organopolysiloxane (B) in the present invention is usually 1,000 to 20,000, preferably 2,000 to 10,000. If it is less than 1,000, the crack resistance and moisture resistance against thermal shock will be poor, and if it exceeds 20,000, the compatibility with the epoxy resin (A) or polyol (D) will be poor. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) using polystyrene as a standard.

Content of (B) in the epoxy resin composition of this invention becomes like this. Preferably it is 0.5-30 weight% with respect to an epoxy resin (A), More preferably, it is 1-15 weight%.
By making the addition amount of (B) 0.5 parts by weight or more, the cured epoxy resin can be toughened, and when it is 30 parts by weight or less, the transparency of the cured epoxy resin can be increased.

  Polyethylene glycol (C), which is the third essential component of the present invention, has a number average molecular weight of 106 to 414, such as diethylene glycol, triethylene glycol; polyoxy having an average degree of polymerization of oxyethylene groups of 4 to 9 Examples include ethylene glycol.

  Of these polyethylene glycols (C), polyoxyethylene glycol having an average degree of polymerization of oxyethylene groups of 4 to 9 is preferred. If average polymerization degree is 4-9, it will be excellent in the thermal stability of the light transmission of epoxy resin hardened | cured material.

  Examples of the polyol (D) having a number average molecular weight of 500 or more, which is the fourth essential component in the present invention, include polyester polyol (D1), polyether polyol (D2), and polycarbonate polyol (D3).

  Examples of the polyester polyol (D1) include a polyol component and a carboxylic acid component, which are synthesized by dehydration esterification reaction, transesterification reaction, lactone ring-opening polymerization, or a combination thereof.

  Examples of the polyether polyol (D2) include reethylene glycol, polypropylene glycol, and polytetramethylene glycol synthesized by ring-opening polymerization of a cyclic ether such as ethylene oxide, propylene oxide, and tetrahydrofuran.

Examples of the polycarbonate polyol (D3) include those synthesized by a carbonate exchange reaction using a phosgene method, a dialkyl carbonate such as dimethyl carbonate and diethyl carbonate.
Specific examples thereof include compounds obtained by reaction of glycols such as 1,4-butanediol, 1,6-hexanediol and diethylene glycol with dialkyl carbonate.

  Of these polyols (D), polycarbonate polyol (D3) is preferred from the viewpoint of thermal stability of light transmission of the cured epoxy resin.

The number average molecular weight of the polyol (D) is 500 or more, preferably 500 to 3,000. In particular, in the case of polycarbonate polyol (D3), the number average molecular weight is preferably 500 to 3,000, more preferably 700 to 1,500.
When the number average molecular weight is less than 500, the cured epoxy product has poor crack resistance and moisture resistance against thermal shock, and when the molecular weight exceeds 3,000, the epoxy resin cured product is thermally stable for light transmission. Sex is reduced.
The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) using polystyrene as a standard.

The polyol (D) in the present invention can be used as long as it has two or more hydroxyl groups in the molecule, but preferably has two to three in the molecule.
Polyol (D) may be used alone or in combination of two or more.

  The polysiloxane compound (E) which is the fifth essential component in the present invention is represented by the general formula (2).

R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (2) are each independently an alkoxyl group, an alkyl group, or a phenyl group.
Examples of the alkoxyl group include a methoxy group, an ethoxy group, and an isopropoxy group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

Among these, from the viewpoint of curability of the epoxy resin, the alkoxyl group is preferably a methoxy group, an ethoxy group, and the alkyl group is preferably a methyl group or ethyl.

Further, R ⁵ in the general formula (2) representing the polysiloxane compound (E) is preferably an alkyl group, at least one of R ⁴ , R ⁶ and R ⁷ is a phenyl group, and the other is an alkyl group or an alkoxyl group. It is preferable that That is, one of R ⁴ , R ⁶ and R ⁷ is a phenyl group and the remaining two are alkyl groups or alkoxyl groups; two of R ⁴ , R ⁶ and R ⁷ are phenyl groups and the remaining one is An alkyl group or an alkoxyl group; a case where R ⁴ , R ⁶ and R ⁷ are all phenyl groups is exemplified.

N in General formula (2) is an integer of 1-20, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-5. When n is 6 or more, unevenness or the like is generated in the cured epoxy resin, and the smoothness of the cured product surface is deteriorated.

In the epoxy resin composition for sealing an optical semiconductor element of the present invention, the epoxy resin (A), the epoxy-modified organopolysiloxane (B), the polyethylene glycol (C), the polyol (D), and the polysiloxane compound (E) are essential. By containing an organoaluminum compound (F) in addition to the components, the curing rate of the epoxy resin composition can be accelerated.

Examples of the organoaluminum compound (F) to be contained for such purpose include alkoxides such as aluminum trimethoxide, aluminum tripropoxide and aluminum tributoxide, halides such as aluminum chloride and aluminum fluoride, tris (ethylacetate). Acetate) aluminum, tris (propylacetate) aluminum, tris (butylacetoacetate) aluminum, propoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, tris (acetoacetonato) aluminum, etc. And chelate compounds, alumina and the like.

  Among these, from the viewpoint of epoxy resin curability, the organoaluminum compound (F) is preferably tris (ethyl acetoacetate) aluminum, tris (propylacetate) aluminum, tris (butylacetoacetate) aluminum, propoxybis ( Chelate compounds such as ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, tris (acetoacetonato) aluminum.

  The epoxy resin composition of the present invention is a range that does not impair the effects of the present invention, and if necessary, a filler, a light diffusing agent, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, A glaze, a leveling agent, an antifoaming agent, a coloring agent, a coloring inhibitor, an antioxidant, a stabilizer, a coupling agent, an acid generator and the like may be blended.

The curing method of the epoxy resin composition of the present invention is a curing method using one or more selected from heat, ultraviolet rays, electron beams and the like.
Since the cured product of the epoxy resin composition of the present invention is excellent in electrical characteristics and other physical characteristics, it is suitable for optical semiconductor element sealing.

The optical semiconductor device of the present invention is an optical semiconductor device made of a constituent material including the above epoxy resin composition and an optical semiconductor element.
Examples of the optical semiconductor element include GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlInGaP, InGaN, GaN, and AlInGaN-based optical semiconductor elements.
When curing an epoxy resin composition used as a sealant, the epoxy resin composition of the present invention is usually encapsulated in a mold or a mold so that a cured product having a desired shape can be obtained. Alternatively, it is applied to a substrate, or an object to be coated is potted in an epoxy resin composition.

In the case of thermosetting, the curing temperature is not particularly limited, and can be performed in the range of 0 ° C to 250 ° C. From the viewpoint of light transmittance after curing and crack resistance against thermal shock, a range of 30 ° C. to 200 ° C. is preferable.
In the case of curing, it may be performed at one stage of temperature rise or at two or more stages. Especially, it is preferable to carry out in 2 to 3 steps from a viewpoint of suppression of cure shrinkage and improvement of moisture resistance.

In the case of ultraviolet ray or electron beam curing, a composition containing a photocationic curing agent in the epoxy resin composition of the present invention is cured by ultraviolet irradiation.
As the photocationic curing agent, aromatic sulfonium salts, aromatic diazonium, aromatic iodonium salts, aromatic selenium salts and the like are used. (For example, benzylmethyl hexafluoroantimonate-P-hydroxyphenylsulfonium, etc.). The content of the photocationic curing agent is 0.01 to 5% by weight based on the weight of the epoxy resin (A).

  The optical semiconductor device obtained as described above has both light transmittance after heat history and crack resistance against thermal shock.

  In addition, the cured product of the epoxy resin composition of the present invention combines the thermal stability of light transmission and crack resistance against thermal shock as described above, and is excellent in other electrical characteristics. It can also be used for other electric / electronic component materials (for example, coating materials, die bonding materials, insulating materials, etc.) other than those for use. Furthermore, it can be used for various epoxy adhesives.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to this.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1 <Synthesis of Epoxy-Modified Organopolysiloxane (B-1)>
After introducing nitrogen into a 1 liter reactor equipped with a stirrer equipped with a thermometer, a condenser, and a dropping funnel, and replacing the air in the reactor with nitrogen, 150.8 g (678 mmol) of hexamethylcyclotrisiloxane, 1,3,5,7 79.4 g (331 mmol), were charged hexamethyldisiloxane 7.0 g (48 mmol) as a chain terminator, after stirring sufficiently, CF ₃ sO ₃ H0.024g (0.16 mmol) was added dropwise.
After dropwise addition of CF ₃ SO ₃ H, the mixture was heated to 80 ° C. and aged for 8 hours. After aging, the catalyst was removed by washing with water, followed by dehydration with sodium sulfate to obtain 320 g of methylhydrogen polysiloxane represented by the following general formula (3).

In a reactor of 1 liter equipped with a stirrer equipped with a thermometer and a dropping funnel, 130 g (1138 mmol) of allyl glycidyl ether, 60 g of toluene, 3 g of ethanol, 1,3-divinyl-1,1,3,3 of chloroplatinic acid -After adding 0.05g of tetramethyldisiloxane complexes and heating to 60 to 70 ° C, 220g of the methylhydrogen polysiloxane obtained above was added dropwise to carry out an addition reaction.
When the solvent was distilled off under reduced pressure at 80 ° C., a transparent epoxy-modified organopolysiloxane (B-1) was obtained.
The number average molecular weight of the obtained (B-1) by GPC was 4,100, and the epoxy equivalent was 250 g / eq.

  It is obtained by curing the epoxy resin composition of the present invention of Examples 1 to 3 blended in the blending ratio described in Table 1 and the epoxy resin composition for comparison of Comparative Examples 1 to 5 under the following conditions. The cured product was measured for light transmission thermal stability, adhesion, and crack resistance by the methods described above. The results are shown in Table 1.

In addition, the symbol of the mixing | blending component in Table 1 represents the following compounds.
<Epoxy resin (A)>
HBE-100 (A-1): glycidyl ether of hydrogenated bisphenol A manufactured by Shin Nippon Rika Co., Ltd .: epoxy equivalent of 213 g / eq
Epicoat YX8040 (A-2): Glycidyl ether of hydrogenated bisphenol A manufactured by Japan Epoxy Resins Co., Ltd .: Epoxy equivalent 1040 g / eq
Celoxide 2021P (A-3): 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate manufactured by Daicel Chemical Industries, Ltd .: epoxy equivalent 130 g / eq
EHPE-3150 (A-4): 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol manufactured by Daicel Chemical Industries, Ltd .: Epoxy equivalent 170 g / Eq

<Epoxy-modified organopolysiloxane (B)>
X22-163B (B′-1): Modified organopolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd .: epoxy equivalent 500 g / eq. [Comparative Example 2 was used instead of the epoxy-modified organopolysiloxane (B-1) of the present invention in that both ends instead of side chains were epoxy-modified. In Comparative Example 5, it was used instead of the main component epoxy resin (A-1). ]
X22-169AS (B′-2): Organopolysiloxane having both ends produced by Shin-Etsu Chemical Co., Ltd., alicyclic epoxy-modified: Epoxy equivalent 500 g / eq. [Used in place of the epoxy-modified organopolysiloxane (B-1) of the present invention in Comparative Example 5 in that the epoxy group was modified with cyclohexene oxide instead of glycidyl ether. ]

<Polyethylene glycol (C)>
PEG200 (C-1): polyethylene glycol PEG400 (C-2) having a number average molecular weight of 200 manufactured by Sanyo Chemical Industries, Ltd .: polyethylene glycol PEG600 (C′-1) having a number average molecular weight of 399, manufactured by Sanyo Chemical Industries, Ltd. ): Polyethylene glycol having a number average molecular weight of 603, manufactured by Sanyo Chemical Industries

<Polyol (D)>
T-5651 (D-1): polycarbonate diol having a number average molecular weight of 1010 manufactured by Asahi Kasei Chemicals Corporation

<Polysiloxane compound (E)>
Dimethoxydiphenylsilane (E-1): SH-6018 (E'-1) manufactured by Tokyo Chemical Industry Co., Ltd .: A polysiloxane compound silanol-modified at both ends manufactured by Toray Dow Corning Silicone Co., Ltd. [Used in place of the alkoxyl group in Comparative Examples 4 and 5 instead of the polysiloxane compound (E-1) of the present invention. ]

The epoxy resin composition was cured by heating to produce cured products, and the thermal stability of light transmission of these cured products, adhesion to the substrate, and crack resistance against thermal shock were evaluated.
The results are shown in Table 1.

<Thermal stability of light transmission>
A 200 μm spacer was used on a glass plate (size: 40 mm × 20 mm) so that the resin thickness was 200 μm, and this was first heated at 100 ° C. × 3 hours, and further heated at 150 ° C. × 5 hours. And cured and removed from the mold to prepare a test piece.
Using this test piece, the transmittance at a wavelength of 400 nm was measured for the test piece after heat treatment in a dryer at 150 ° C. for 72 hours. A spectrophotometer (UV-2400PC, manufactured by Shimadzu Corporation) was used for the measurement of transmittance.

<Adhesion>
An epoxy resin is coated on a glass plate (size: 40 mm × 20 mm), and a square silicon chip (2 mm × 2 mm × 0.3 mm) is placed on the coated surface so that the bonding area is 2 mm × 2 mm. The epoxy resin was cured at 150 ° C. for 3 hours and then 150 ° C. for 5 hours, and a silicon chip was bonded.
After that, using a die shear tester (Arctech, model number: DAGE 4000), continue to apply the load from the side of the silicon chip at the speed of 1 mm / sec until the epoxy resin breaks down or the interface peels off, sharing the maximum load. Adhesion was evaluated according to the following evaluation criteria as strength.
○: Shear strength is 30 N / mm ² or more Δ: Shear strength is 5-30 N / mm ²
×: The shear strength is less than 5 N / mm ²

<Crack resistance>
Place one brass washer with an inner diameter of 3 mm, an outer diameter of 10 mm, and a thickness of 1 mm into a cylindrical silicone container of diameter 30 ± 0.5 mm × height 10 mm so that the epoxy resin composition has a depth of 3 mm. After pouring and heating at 100 ° C. for 3 hours, it was further cured by heating at 150 ° C. for 5 hours. Thereafter, the cured product was demolded. 30 of these were created.
Repeated 1000 cycles of −50 ° C. × 15 minutes and 120 ° C. × 15 minutes with a vapor-phase thermal shock tester WINTECH (manufactured by ETAC). Crack resistance was evaluated according to the evaluation criteria.
○: The rate of occurrence of cracked samples is less than 10%. Δ: The rate of occurrence of cracked samples is 10 to 50%.
×: The rate of occurrence of cracked samples is 50% or more

As is apparent from the results in Table 1, the cured products of the epoxy resin compositions of Examples 1 to 3 all have high light transmittance after heat treatment, and are excellent in adhesion and crack resistance.
On the other hand, Comparative Examples 1, 2, and 4 that do not contain the epoxy-modified organosiloxane (B) of the present invention have low crack resistance because they cannot relieve the generated internal stress.
Further, Comparative Example 2 using an epoxy-modified organosiloxane (B′-1) having an epoxy group only at both ends instead of the epoxy-modified organosiloxane (B) of the present invention has poor adhesion and crack resistance. It is enough.
In Comparative Example 3 using (C′-1) in which the number average molecular weight of the polyethylene glycol is outside the range of the present invention, although the adhesion and crack resistance are excellent, the thermal stability of light transmission is lowered.
In Comparative Example 5 in which an epoxy-modified organopolysiloxane itself is used as the main component epoxy resin instead of a normal epoxy resin, the adhesion is extremely low.

  The cured product from the epoxy resin composition of the present invention has thermal stability of light transmission, adhesion, and crack resistance against thermal shock, so that it can be used for paints, adhesives, semiconductor sealing materials, and electrical / electronic applications. It is suitable for various fields such as parts materials. In particular, it is useful as an optical semiconductor element sealing resin.

Claims (9)

Epoxy resin (A), epoxy-modified organopolysiloxane (B) having a chemical structure represented by general formula (1), polyethylene glycol (C) having a number average molecular weight of 106 to 414, polyol having a number average molecular weight of 500 or more ( D) and a polysiloxane compound (E) having one or more alkoxyl groups as an essential component, an epoxy resin composition for encapsulating an optical semiconductor element.

[In General Formula (1), each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b are each independently an integer of 1 to 100, and a / b is 0.1 -10. m is an integer of 1-50. The bond form in [] may be either random bond, block bond, or a combination thereof. R ² is an alkylene group or an oxyalkylene group. R ³ is each independently an alkyl group having 1 to 6 carbon atoms. ]   2. The epoxy resin composition for sealing an optical semiconductor element according to claim 1, wherein the epoxy-modified organopolysiloxane (B) has a number average molecular weight of 1,000 to 20,000.   3. The epoxy resin composition for sealing an optical semiconductor element according to claim 1, wherein a / b of the epoxy-modified organopolysiloxane (B) is 0.1-4.   4. The epoxy resin composition for sealing an optical semiconductor element according to claim 1, wherein the content of the epoxy-modified organopolysiloxane (B) is 0.5 to 30 wt% with respect to the epoxy resin (A). .   The epoxy resin composition for optical semiconductor element sealing according to any one of claims 1 to 4, wherein the epoxy resin (A) is an alicyclic epoxy resin. The optical semiconductor element sealing according to any one of claims 1 to 5, wherein the polysiloxane compound (E) is a siloxane compound having one or more alkoxyl groups and one or more phenyl groups represented by the general formula (2). Epoxy resin composition.

[In General Formula (2), n is an integer of 1 to 20; R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkoxyl group, an alkyl group, or a phenyl group. ] R ⁵ in the general formula (2) representing the polysiloxane compound (E) is an alkyl group; at least one of R ⁴ , R ⁶ and R ⁷ is a phenyl group, and the other is an alkyl group or an alkoxyl group. Item 7. An epoxy resin composition for sealing an optical semiconductor element according to any one of Items 1 to 6.   Furthermore, the epoxy resin composition for optical semiconductor element sealing of any one of Claims 1-7 containing an organoaluminum compound (F).   The optical semiconductor device formed by hardening | curing the epoxy resin composition for optical semiconductor element sealing in any one of Claims 1-8, and sealing an optical semiconductor element.